Removable film forming gel compositions featuring adhesion promoters

ABSTRACT

Film-forming gel compositions, useful in creating conformable and flexible gel bandages, can be formulate from a film-forming polymer, an amine-rich adhesion promoter, and a volatile solvent. The gel compositions form relatively thick films when dried on tissue, and can exhibit enhanced breathability to promote wound healing.

SUMMARY

The present disclosure provides easy to apply gel compositions that dryto form durable film bandages and other tissues protectants. Thefilm-forming, gel compositions of the present disclosure can beflexible, breathable, waterproof, non-stinging, gentle to skin, and easyto remove by peeling or other wearer generated force. The gelcompositions, when dried, possess enhanced cohesion and integrity. Ifdesired, the gel compositions are capable of absorbing moisture andwound exudate, particularly blood. Accordingly, the film-formingcompositions are particularly well suited for use as a liquid bandage orskin protectant. The gel compositions are useful for protecting ortreating skin, tissues, organs, nails, hydrated tissues and mucousmembranes, e.g., bleeding injuries, surgical site, skin ulcers, coldsores, cuts, rashes, abrasions, incisions and blisters, abraded gums andother oral surfaces, hemorrhoids and abraded body areas, and othermucosal membrane incisions and wounds.

In certain advantageous implementations, neither the gel composition northe subsequently-formed films irritate the skin and other tissue duringapplication, drying, or during use after drying. The bandages createdare desirably substantially painless while worn and can be easilyremoved by peeling, if desired, substantially without pain ordisturbance of the wound site. The dried bandages formed can exhibithigh water vapor transmission throughout. The gel composition, whenapplied over surfaces moist with blood or body fluids, can form a tough,lightly adherent film that can, in certain circumstances, absorb andretain volumes of exudate.

Notably, the gel compositions of the present disclosure can dry to arelatively thick, flexible film with the desirable wound healingproperties (e.g., breathable, flexible, non-stinging) in a singleapplication. In particular, it is possible that a gel compositionapplied at a 50-120 mil coating thickness to skin at room temperature,an adherent film can form having a thickness of at least 2 mils, atleast 3 mils, at least 4 mils, at least 5 mils, or at least 6 mils. Oncedried on skin, the gel compositions exhibit a 180 degree peel adhesionfrom human skin of no greater than 900 grams per square inch accordingto a Skin Adhesion Test and a keratin removal level of no greater than40% according to a Skin Removal Test. Accordingly, the dried films canbe removed by application of force without substantial damage to theunderlying skin or wound site.

In one aspect, the gel composition includes a film-forming polymer, acompatible tackifier, an antiseptic, a volatile solvent, and optionallyat least one of a cationic polymer acting as a coagulant and anamine-rich adhesion promoter. At least the film-forming polymer and thetackifier are typically soluble in the solvent. The gel composition maybe silicone-based, in that the film-forming material includes asilicone-containing polymer. The film-forming polymer may be composed ofsegmented siloxane copolymers, including silicone polyurea blockcopolymers and polydiorganosiloxane polyoxamide block copolymers. Thesepolymeric materials are typically non-adhesive materials, often havingrelease properties, and can be formulated with silicate tackifyingresins (such as MQ resins), amine-rich adhesion promoters, or certaincoagulants. A particularly suitable film-forming polymer is apolydiorganosiloxane polyoxamide.

In one aspect, the present disclosure provides a film-forming gelcomposition for use as a conformable film bandage, the compositionincluding a silicone-containing, film-forming polymer; an amine-richadhesion promoter, and a volatile solvent. A film cast from thecomposition is self-supporting on a biological substrate and can bepeeled off the substrate without substantially compromising theintegrity of the film such that at least a portion of the film isremovable in a single continuous layer.

In yet another aspect, the present disclosure provides a film useful asa conformable bandage, wherein the film exhibits an upright MVTR of atleast 300 g/m²/24 hours, a Skin Adhesion of at least 50 g/inch and nogreater than 900 g/inch, an elongation of at least 100%, and an ultimatetensile strength of at least 0.3 MPa. At least a portion of the film hasa thickness of at least 2 mils and no greater than 20 mils, and the filmis self-supporting and consists of a single layer.

The film can include: (a) (a) 50-75 wt. % film-forming polymer, (b)0.1-30 wt. % filler, and (c) 10-60 wt. % amine-rich adhesion promoter,based on the weight of the film.

The terms “comprises” and variations thereof do not have a limitingmeaning where these terms appear in the description and claims.

The words “preferred” and “preferably” refer to embodiments of theinvention that may afford certain benefits, under certain circumstances.However, other embodiments may also be preferred, under the same orother circumstances. Furthermore, the recitation of one or morepreferred embodiments does not imply that other embodiments are notuseful, and is not intended to exclude other embodiments from the scopeof the invention.

As recited herein, all numbers should be considered modified by the term“about” unless stated otherwise.

As used herein, “a,” “an,” “the,” “at least one,” and “one or more” areused interchangeably. Thus, for example, a composition comprising “a”cationic antimicrobial agent can be interpreted as a gel compositioncomprising “one or more” cationic antimicrobial agents.

Also herein, the recitations of numerical ranges by endpoints includeall numbers subsumed within that range (e.g., 1 to 5 includes 1, 1.5, 2,2.75, 3, 3.80, 4, 5, etc.).

As used herein as a modifier to a property or attribute, the term“generally”, unless otherwise specifically defined, means that theproperty or attribute would be readily recognizable by a person ofordinary skill but without requiring absolute precision or a perfectmatch (e.g., within +/−20% for quantifiable properties). The term“substantially”, unless otherwise specifically defined, means to a highdegree of approximation (e.g., within +/−10% for quantifiableproperties) but again without requiring absolute precision or a perfectmatch. Terms such as same, equal, uniform, constant, strictly, and thelike, are understood to be within the usual tolerances or measuringerror applicable to the particular circumstance rather than requiringabsolute precision or a perfect match.

The term “polydiorganosiloxane” refers to a divalent segment of formula

where each R¹ is independently an alkyl, haloalkyl, aralkyl, alkenyl,aryl, or aryl substituted with an alkyl, alkoxy, or halo; each Y isindependently an alkylene, aralkylene, or a combination thereof; andsubscript n is independently an integer of 0 to 1500.

As used herein, “film-forming” refers to a composition when allowed todry under ambient conditions (e.g., 23° C. and 50% relative humidity(RH)) on skin or mucosal tissue forms a continuous layer that does notflake off after simple flexing of the tissue.

As used herein, “moisture vapor transmission rate” (MVTR), also referredto as “water vapor transmission rate” (WVTR), is a measure of thepassage of water vapor through a substance.

As used herein “ready to use” refers to the composition intended to beapplied (e.g., to skin or mucosal tissue) without dilution. It should beunderstood that (unless otherwise specified) the listed amounts of allidentified components are for “ready to use” gel compositions.

As used herein, “active kill” means to render a microorganismineffective by killing (e.g., bacteria and fungi) or otherwise renderinginactive (e.g., viruses) and may be distinguished from disruptingmicroorganism adhesion or mere bacteriostatic activity. Typically, anactive kill results in at least a 0.5 log reduction using theAntimicrobial Efficacy Test described herein, and is desirably at leasta 1 log reduction, more preferably at least a 2 log reduction, even morepreferably at least a 3 log reduction. It should be understood that inthe compositions described herein, the concentrations or amounts of thecomponents, when considered separately, may not kill to an acceptablelevel, or may not kill as broad a spectrum of undesired microorganisms,or may not kill as fast; however, when used together such componentsprovide an enhanced (preferably synergistic) antimicrobial activity (ascompared to the same components used alone under the same conditions).

The above summary of the present disclosure is not intended to describeeach disclosed embodiment or every implementation of the presentinvention. The description that follows more particularly exemplifiesillustrative embodiments. In several places throughout the application,guidance is provided through lists of examples, which examples can beused in various combinations. In each instance, the recited list servesonly as a representative group and should not be interpreted as anexhaustive list.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a flow chart of a method of applying a gel composition of thepresent disclosure to a target site;

FIG. 2 is a flow chart of another method of applying a gel compositionof the present disclosure to a target site;

FIG. 3 is a flow chart of another method of applying a gel compositionof the present disclosure to a target site;

FIG. 4 is an isometric view of an applicator tip suitable for dispensinggel compositions according to methods of the present disclosure;

FIG. 5 is an isometric view of another applicator tip suitable fordispensing gel compositions according to methods of the presentdisclosure;

FIG. 6 is a flow chart of another method of applying a gel compositionof the present disclosure to a target site.

While the above-identified figures set forth several embodiments of thedisclosure other embodiments are also contemplated, as noted in thedescription. In all cases, this disclosure presents the invention by wayof representation and not limitation. It should be understood thatnumerous other modifications and embodiments can be devised by thoseskilled in the art, which fall within the scope and spirit of theprinciples of the invention.

DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS

The present disclosure provides myriad flexible, breathable,non-stinging, gentle to skin, self-supporting, and film-formingcompositions. The gel composition used in forming a bandage or otherprotectant typically includes a silicone-containing, film-formingpolymer, a tackifier, a coagulant, an antiseptic, and a volatilesolvent. Other compositions may exclude antiseptic, coagulant, or both.The gel compositions of the present disclosure may also include fillers,antibiotics, surfactants, and other additives to enhance user comfort ortreatment (e.g., release agents to the underlying area of coveredtissue). It is a particular feature of the disclosure that the gelmaterials can act at room temperature (20° C.) when applied to tissuesof a user to form films in minutes or less. The films are conformable,comfortable and can be elastic and flexible. The films do notsignificantly irritate the skin and mucous membrane when depositedduring application and in use after drying. The dried films aresubstantially painless and can be removed substantially without pain.The dried bandages formed are substantially non-water sensitive and havehigh moisture vapor transmission therethrough. The bandages can formwhen applied over surfaces wet with water, blood or body fluids, inshort times at standard room temperature and reasonable variantsthereof. The use of gel compositions over certain bleeding or exudatingwounds provides a stark advantage over previously availablecompositions, which rely on the maintenance of dry or drier targetsurfaces. The compositions of the present disclosure also tend to beeasier to coat in relatively thicker applications, which are morevisible to the user and consequently easier to remove. The combinationof features allows the compositions of the present disclosure to coverand protect myriad open wounds. Protectable wounds include, but are notlimited to, abrasions, lacerations, scrapes, punctures, burns, andpressure sores.

Certain gel compositions of the present disclosure, particularlyantiseptic compositions, include one or more of the followingcharacteristics: relatively high levels of bacterial kill if anantimicrobial agent is present (or if the composition is inherentlyantimicrobial); relatively short dry times; generally clear viewing ofthe underlying tissue; good adhesion to the skin when dry; little or notack when dry; capable of releasing an active agent such as anantimicrobial agent or a coagulant; and can be removed relatively easilyin a single continuous film, preferably without the need for organicsolvent-based removers or other dissolution.

In other implementations, the gel compositions may be used to securemedical articles to the skin or other tissue. Useful medical articlesthat can be secured by dried films resulting from such gel compositionsinclude, but are not limited to: nasal gastric tubes, blood streamcatheters, dialysis catheters and tubing stents, surgical tools,tympanoplasty tubes, shunts including shunts for hydrocephalus,post-surgical drain tubes and drain devices, urinary catheters,endotraecheal tubes, other implantable devices, and other indwellingdevices.

Dry times of the film of the present disclosure are preferably nogreater than about 5 minutes, more preferably no greater than about 3minutes, even more preferably no greater than about 2 minutes, and mostpreferably no greater than about 1.5 minutes on skin measured at 23° C.at 45-55% relative humidity. Dry time can be considered as the minimumtime for a composition applied at a defined coat weight to be visiblydry, demonstrate no transfer of the composition to a latex glovedcovered hand, and have a minimum level of tack. Dry time of a givencomposition can be measured under ASTM D 5895-13, particularly with acircular time drying recorder (Test Method B). Dry time measured underthis method may be longer than those experienced on skin. Note that thecomposition may be tack free (in that no composition transfers to agloved hand) and yet still be not completely dry. Accordingly, tack freetimes are preferably no greater than about 2 minutes, no greater thanabout 1 minutes, and in some implementations no greater than about 30seconds.

The desired specific viscosity of the gel composition depends, in part,on the intended application. For example, where application is to bemade to a specific position on the skin (e.g., elbow surfaces, kneesurfaces and the like), higher viscosity compositions are preferred toprevent “running” of the compositions to unintended locations. Preferredcompositions, in present circumstances, of the present disclosure alsopossess viscosities that ensure the applied gel easily conforms totissues while drying, does not run, and forms a relatively thick film.For conformable films the viscosity of a gel composition is at least20,000 Centipoise (cps), at least 50,000 cps, at least 60,000 cps and inyet other embodiments at least 70,000 cps. To avoid undue difficulty inapplying the gel composition to the target area, the viscosity is nogreater than about 1,100,000 cps, no greater than about 800,000 cps, nogreater than about 600,000 cps, no greater than about 400,000 cps and inyet other implementations no greater than about 250,000 cps whenmeasured at 23° C. using a Brookfield LVT viscometer and the proceduredescribed in the Examples Section. This viscosity range can, in certaincircumstances, ensure that the compositions can be applied to the skinin a uniform film that will dry rapidly and maintain structuralintegrity throughout wear. Furthermore, certain compositions may benefitfrom higher viscosities as applied, in that (along with other variables)the higher viscosity composition may exhibit less settling (i.e., fewerconstituents settling out of an otherwise dissolved or dispersedcomposition). Applicants have found that certain gel compositions withspecific viscosity in the range of 200,000 to 500,000 cps (andparticularly 250,000 to 400,000 cps) can be easier to apply, position,and dry while still resulting in a protective covering film exhibitingthe characteristics and benefits described below.

The dried films of compositions of the present disclosure are generallyflexible and durable, and relatively lightly adherent. That is, they donot crack or flake off as brittle films might do and they remain on skinwithout needing desquamation for removal. Significantly, thefilm-forming polymer and compatible tackifier contribute to achieving adelicate balance between low tack, breathability, and flexibility. Thecomposition are accordingly useful on surface areas exposed to highlevels of movement, e.g., knuckles, knees, elbows, feet and the like. Afilm of dried gel composition can have a thickness of at least 1, atleast 1.5, 2, 4, 8 mils and typically no greater than 25, 20, 15 mils,and 10 mils. As used herein, the term “mil” refers to 0.001 inch and 1mil is equal to about 0.0025 centimeters or about 0.025 millimeters orabout 25 micrometers. While the gel compositions of the presentdisclosure can be coated in such a manner as to form a film having auniform or substantially uniform thickness, variations in, for example,the pressure applied or the applicator used can result in variablethickness throughout the film layer. In presently preferredimplementations, the thickness of the film over the target (e.g., woundor skin lesion) is at least 2 mils thick, while areas of the filmsurrounding the target (e.g., unblemished tissue) may exhibit arelatively thinner film thickness. Certain methods of application,including those described below, can assist in providing a more uniformthickness to normalize dry time and enhance protection.

The conformability and durability properties of the dried films can bedetermined in part by standard tensile and elongation testing. Theelongation of the dried film can range from 50, 75, or 100% to 1400%. Insome embodiments, the elongation is at least 100% and no greater than600%. The ultimate tensile strength is typically at least 0.2, 0.3, or0.4 MPa and is typically no greater than 2 MPa. In some embodiments, theultimate tensile strength is no greater than 2, 1.5, or 1 MPa. TheYoung's elastic modulus is typically at least 0.5, 0.6, 0.7, 0.8, 0.9 or1 MPa and is typically no greater than about 2 MPa. In some embodiments,the Young's elastic modulus of a tested film is at least 0.7 MPa andtypically no greater than 1.5 MPa. Such tensile and elongationproperties can be measured, for example, by the methods outlined in ASTMD882-12.

The dried films of compositions of the present disclosure are alsorelatively lightly adherent. Suitable films typically exhibit a peeladhesion to skin according to the Skin Adhesion Test, described below,of at least 25 g/inch, in some embodiments at least 50 g/inch, and insome embodiments at least 75 g/inch. Suitable dried films typicallyexhibit a peel adhesion according to the Skin Adhesion Test of nogreater than 1000 g/inch, in some embodiments no greater than 900g/inch, in some embodiments no greater than 600 g/inch. A relativelylight adherent film within the above range is typically capable ofremaining on the surface to which is applied during desired wear periodand is advantageously also capable of being pulled away (e.g., with userapplied force) without causing rupture or tearing of the surface: forbiological surfaces such as skin, without removing portions of theepidermis or damaging skin, scars or tissue underneath the film. Thiscan be a significant advantage over silicone-containing liquid bandagesof the prior art, which often rely on the normal desquamation at theapplied site for adequate removal (see e.g., U.S. Pat. No. 8,197,803(Salamone et al.)).

The dried films cast from the gel compositions of the present disclosurecan exhibit moisture vapor transmission rates of at least 300 g/m²/24,thus both preventing dehydration of the wounded area and promoting moistwound healing. Herein, dry MVTR (or upright MVTR) of the dried filmbandage is measured by ASTM E-96-80 at 40° C. and 20% relative humidityusing an upright cup method. Wet MVTR (or inverted MVTR) is measured bythe same method except that the sample jars are inverted so the water isin direct contact with the test sample.

Factors influencing the MVTR of a dried film from the inventive gelcompositions include, but are not limited to, the thickness of the filmlayer on the tissue, relative amount of solids in the gel compositionbefore application, the formulation of the gel composition, theviscosity of the gel composition, and the coating structure (i.e.,continuous film, or pattern) of the gel. The dried films cast from thegel compositions of the present disclosure exhibit a dry MVTR of atleast 300 g/m²/24 hours, more preferably at least 500 g/m²/24 hours,even more preferably at least 1000 g/m²/24 hours, and even morepreferably at least 1500 g/m²/24 hours. The dried films preferably havea wet MVTR of at least 500 g/m2/24 hours, more preferably at least 900g/m2/24 hours, even more preferably at least 1000 g/m2/24 hours, andeven more preferably at least 1300 g/m2/24 hours. Different regions ofthe film may include different dry and/or wet MVTR values.

Surprisingly, the gel compositions exhibit the above, enhanced MVTRseven when applied at the greater coating weight with higher percentsolids (and having resultant greater film thickness) than common liquidbandages. Thanks in part to this breathability and other components, thedried films of the present composition can enhance wound healing byincreasing the rate of wound reepithelization. The gel compositions ofthis disclosure may be applied to the skin, mucous membranes, etc. inliquid form by utilization of a brush, rod, finger, sponge, cloth,dropper, etc.; in spray or mist form; or any other usable technique forapplying a liquid to a surface such as a wipe, swab or solid paddleapplicator. In certain advantageous implementations, the compositionsare applied at a wet coat thickness between 25 mils and 150 mils, and incertain implementations between 40 mils and 100 mils. It is typicallypreferred, after drying, that the resultant films have a thickness offrom about 2 to about 20 mils. A relatively thicker film can beadvantageous for site protection and ease of removal, but will typicallyrequire a longer dry time than relatively thinner films of the samecomposition. Overall, in one embodiment, the total solids content of thegel composition is at least 15 wt. %, and in one embodiment is at least20% wt., and in one embodiment is less than 35% wt. of the total gelcomposition.

Advantageously, the dried films of the present disclosure areself-supporting after a single application of gel composition. As usedherein, a “self-supporting” film exhibits the desired combination ofbreathability, durability, and flexibility in a single strata andwithout the application of additional layers of gel composition on anouter surface of a dried film. Moreover, a “self-supporting” film doesnot require an additional, flexible backing for continued wear (i.e., atleast 8 hours of continuous existence on the skin or other targettissues). One presently desirable film exhibits an upright MVTR of atleast 300 g/m²/24 hours, a film thickness of at least 2 mils and nogreater than 20 mils, a skin adhesion of no greater than 900 g/inch, anelongation of at least 100%, and an ultimate tensile strength of atleast 0.4 MPa.

Typical gel compositions can comprise (a) 10-15 wt. % film-formingpolymer, (b) 3-5 wt. % tackifier (c) 0-0.3 wt. % antiseptic, (d) 0-3%filler, (e) 60-80 wt. % solvent, (f) 0-5 wt. % cationic polymer, andoptionally (g) 0.1-2 wt. % silicone surfactant, based on the totalweight of the gel composition.

Dried films of the present disclosure typically comprise (a) 50-75%film-forming polymer, (b) 15-30 wt. % tackifier (c) 0.1-0.5 wt. %antiseptic, (d) 0-12 wt. % filler, and (e) 0-20 wt. % cationic polymerand optionally (f) 0.5-15 wt. % silicone surfactant, based on the totalweight of the dried film.

Film-Forming Polymer

In one aspect, the gel compositions of the present disclosure include afilm-forming polymer which is capable of forming a substantiallycontinuous layer upon drying. Suitable film-forming polymers are atleast partially soluble in a volatile solvent, and includesilicone-containing polymers. Particularly suitable silicone containingpolymers include polysiloxane polyamides, silicone polyureas, andsilicone polyamines.

The film-forming polymer is typically soluble in the solvent system usedin the gel composition. As used herein, a polymer is “soluble” or“solubilized” if the amount of polymer present in the solvent system iscompletely dissolved in the solvent system without the polymer forming aprecipitate or visible, swollen gel particles in solution. As usedherein, the term “solubility limit” is the maximum amount, measured as apercentage of the total weight of the solution, of a given polymer thatcan be dissolved in a given solvent system. For example, thefilm-forming polymer can have a solubility limit of at least 5 wt. %, atleast 10 wt. %, at least 15 wt. %, at least 20 wt. %, in thehexamethyldisiloxane (HMDS), isooctane or any other solvent systemdescribed herein, based on the total weight of the gel composition.

Silicone-containing polymers useful for practicing the presentdisclosure may have an intrinsic viscosity (“IV”) of at least 0.9, atleast 1.45, at least 1.68, or at least 1.8. The silicone containingpolymer typically has an intrinsic viscosity less than 3, as polymershaving an intrinsic viscosity above 3 can be difficult to solubilize incertain circumstances. Lower IV polymers have notably higher solubilityin the solvents and solvent systems and hence, while they can be filmformers, they can be slower to dry and remain tacky after application.The IV of the polymers may be controlled by varying initiator, initiatorconcentration, reaction temperature, reaction solvent, reaction method,and other parameters known to those skilled in the art.

Siloxanes & Polysiloxane Polyamides

Siloxane polymers have unique properties derived mainly from thephysical and chemical characteristics of the siloxane bond. Theseproperties include low glass transition temperature, thermal andoxidative stability, resistance to ultraviolet radiation, low surfaceenergy and hydrophobicity. The siloxane polymers, however, often lacktensile strength. The low tensile strength of the siloxane polymers canbe improved by forming block copolymers. Some block copolymers contain a“soft” siloxane polymeric block or segment and any of a variety of“hard” blocks or segments. Particularly suitable elastomericsiloxane-based elastomeric polymers are the segmented polymers ofFormula 1 and Formula 2 below.

In some embodiments, the silicone-containing polymer is a linearpolydiorganosiloxane, a linear polydiorganosiloxane polyamide blockcopolymer or a polydiorganosiloxane urethane-containing copolymer, butother silicone-containing polymers may be useful.

A polydiorganosiloxane can have a variety of organic substituents on thesilicon carbon atoms of the polysiloxane. For example, each organicsubstituent can be is independently an alkyl, haloalkyl, arylalkylenyl,alkylarylenyl, alkenyl, aryl, or aryl substituted with an alkyl, alkoxy,or halo. The polydiorganosiloxane may have repeating units of thegeneral formula (Si(R⁷)₂O—) wherein R⁷ is as defined below for any ofthe embodiments of R⁷ in Formula I. Examples include dimethylsilicones,diethylsilicones, and diphenylsilicones. In some embodiments, at least40 percent, and in some embodiments at least 50 percent, at least 60percent, at least 70 percent, at least 80 percent, at least 90 percent,at least 95 percent, at least 98 percent, or at least 99 percent of theR⁷ groups can be phenyl, methyl, or combinations thereof. In someembodiments, at least 40 percent, at least 50 percent, at least 60percent, at least 70 percent, at least 80 percent, at least 90 percent,at least 95 percent, at least 98 percent, or at least 99 percent of theR⁷ groups are methyl. High molecular weight polydimethylsiloxane (PDMS)is commercially available, for example, from Dow Corning Corporation,Midland, Mich.

A linear, polydiorganosiloxane polyamide block copolymer useful forpracticing the present disclosure contains at least two repeat units ofFormula I:

In this formula, each R⁷ is independently an alkyl, haloalkyl,arylalkylenyl, alkylarylenyl, alkenyl, aryl, or aryl substituted with analkyl, alkoxy, or halo. Each Y is independently an alkylene,arylalkylene, alkylarylene, or a combination thereof. Subscript n isindependently in a range from 0 to 1500 and subscript p is in a rangefrom 1 to 10. Each group B is independently a covalent bond, analkylene, an arylalkylene, an alkylarylene, an arylene, or a combinationthereof. When each group B is a covalent bond, the polydiorganosiloxanepolyamide block copolymer of Formula I is referred to as apolydiorganosiloxane polyoxamide block copolymer.

Group G is a divalent group that is the residue unit that is equal to adiamine of formula

R⁸HN-G-NHR⁸ minus the two —NHR⁸ groups. Group R⁸ is hydrogen or alkyl(e.g., an alkyl having 1 to 10, 1 to 6, or 1 to 4 carbon atoms) or R⁸taken together with G and with the nitrogen to which they are bothattached forms a heterocyclic group. Each asterisk (*) indicates a siteof attachment of the repeat unit to another group in the copolymer suchas, for example, another repeat unit of Formula I.

Suitable alkyl groups for R⁷ in Formula I typically have 1 to 10, 1 to6, or 1 to 4 carbon atoms. Examples of useful alkyl groups includemethyl, ethyl, isopropyl, n-propyl, n-butyl, and iso-butyl. Suitablehaloalkyl groups for R⁷ often have only a portion of the hydrogen atomsof the corresponding alkyl group replaced with a halogen. Examples ofhaloalkyl groups include chloroalkyl and fluoroalkyl groups with 1 to 3halo atoms and 3 to 10 carbon atoms. Suitable alkenyl groups for R⁷often have 2 to 10 carbon atoms. Examples of alkenyl groups often have 2to 8, 2 to 6, or 2 to 4 carbon atoms such as ethenyl, n-propenyl, andn-butenyl. Suitable aryl groups for R⁷ often have 6 to 12 carbon atoms.Phenyl is an example of an aryl group. The aryl group can beunsubstituted or substituted with an alkyl (i.e., it may be analklyarylenyl group) (the alkyl group may be, e.g., an alkyl having 1 to10 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms), an alkoxy(e.g., an alkoxy having 1 to 10 carbon atoms, 1 to 6 carbon atoms, or 1to 4 carbon atoms), or halo (e.g., chloro, bromo, or fluoro). Suitablearylalkylenyl and alkylarylenyl groups for R⁷ usually have an alkylenegroup with 1 to 10 carbon atoms and an aryl group with 6 to 12 carbonatoms. In some arylalkylenyl and alkylarylenyl groups, the aryl group isphenyl and the alkylene group has 1 to 10 carbon atoms, 1 to 6 carbonatoms, or 1 to 4 carbon atom. For example, R⁷ may be an arylalkylenylgroup where any of these alkylene groups is bonded to a phenyl group.

In some embodiments, in some repeat units of Formula I, at least 40percent, and in some embodiments at least 50 percent, of the R⁷ groupsare phenyl, methyl, or combinations thereof. For example, at least 60percent, at least 70 percent, at least 80 percent, at least 90 percent,at least 95 percent, at least 98 percent, or at least 99 percent of theR⁷ groups can be phenyl, methyl, or combinations thereof. In someembodiments, in some repeat units of Formula I, at least 40 percent, andin some embodiments at least 50 percent, of the R⁷ groups are methyl.For example, at least 60 percent, at least 70 percent, at least 80percent, at least 90 percent, at least 95 percent, at least 98 percent,or at least 99 percent of the R⁷ groups can be methyl. The remaining R⁷groups can be selected from an alkyl having at least two carbon atoms,haloalkyl, arylalkylenyl, alkylarylenyl, alkenyl, aryl, or arylsubstituted with an alkyl, alkoxy, or halo.

Each Y in Formula I is independently an alkylene, arylalkylene,alkylarylene, or a combination thereof. Suitable alkylene groupstypically have up to 10 carbon atoms, up to 8 carbon atoms, up to 6carbon atoms, or up to 4 carbon atoms. Examples of alkylene groupsinclude methylene, ethylene, propylene, butylene, and the like. Suitablearylalkylene and alkylarylene groups usually have an arylene group with6 to 12 carbon atoms bonded to an alkylene group with 1 to 10 carbonatoms. In some arylalkylene and alkylarylene groups, the arylene portionis phenylene. That is, the divalent arylalkylene or alkylarylene grouphas phenylene bonded to an alkylene having 1 to 10, 1 to 8, 1 to 6, or 1to 4 carbon atoms. As used herein with reference to group Y, “acombination thereof” refers to a combination of two or more groupsselected from an alkylene and arylalkylene or alkylarylene group. Acombination can be, for example, a single alkylarylene bonded to asingle alkylene (e.g., alkylene-arylene-alkylene). In one example of analkylene-arylene-alkylene combination, the arylene is phenylene and eachalkylene has 1 to 10, 1 to 6, or 1 to 4 carbon atoms.

Each subscript n in Formula I is independently in a range from 0 to1500. For example, subscript n can be up to 1000, up to 500, up to 400,up to 300, up to 200, up to 100, up to 80, up to 60, up to 40, up to 20,or up to 10. The value of n is often at least 1, at least 2, at least 3,at least 5, at least 10, at least 20, or at least 40. For example,subscript n can be in the range of 40 to 1500, 0 to 1000, 40 to 1000, 0to 500, 1 to 500, 40 to 500, 1 to 400, 1 to 300, 1 to 200, 1 to 100, 1to 80, 1 to 40, or 1 to 20.

The subscript p is in a range from 1 to 10. For example, the value of pis often an integer up to 9, up to 8, up to 7, up to 6, up to 5, up to4, up to 3, or up to 2. The value of p can be in the range of 1 to 8, 1to 6, or 1 to 4.

Group G in Formula I is a residual unit that is equal to a diaminecompound of formula

R⁸HN-G-NHR⁸ minus the two amino groups (i.e., —NHR⁸ groups). The diaminecan have primary or secondary amino groups. Group R⁸ is hydrogen oralkyl (e.g., an alkyl having 1 to 10, 1 to 6, or 1 to 4 carbon atoms) orR⁸ taken together with G and with the nitrogen to which they are bothattached forms a heterocyclic group (e.g., a 5- to 7-membered ring). Insome embodiments, R⁸HN-G-NHR⁸ is piperazine. In some embodiments, R⁸ ishydrogen or an alkyl. In some embodiments, both of the amino groups ofthe diamine are primary amino groups (i.e., both R⁸ groups are hydrogen)and the diamine is represented by formula H₂N-G-NH₂.

In some embodiments, G is an alkylene, heteroalkylene,polydiorganosiloxane, arylene, arylalkylene, alkylarylene, or acombination thereof. Suitable alkylenes often have 2 to 10, 2 to 6, or 2to 4 carbon atoms. Examples of alkylene groups include ethylene,propylene, and butylene. Suitable heteroalkylenes are oftenpolyoxyalkylenes such as polyoxyethylene having at least 2 ethyleneunits, polyoxypropylene having at least 2 propylene units, or copolymersthereof. Examples of polydiorganosiloxanes include polydimethylsiloxaneswith alkylene terminal groups. Suitable arylalkylene groups usuallycontain an arylene group having 6 to 12 carbon atoms bonded to analkylene group having 1 to 10 carbon atoms. Some examples ofarylalkylene groups are phenylene-alkylene where the phenylene is bondedto an alkylene having 1 to 10 carbon atoms, 1 to 8 carbon atoms, 1 to 6carbon atoms, or 1 to 4 carbon atoms. Some examples of alkylarylenegroups are alkylene-phenylene where the alkylene having 1 to 10 carbonatoms, 1 to 8 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atomsis bonded to a phenylene. As used herein with reference to group G, “acombination thereof” refers to a combination of two or more groupsselected from an alkylene, heteroalkylene, polydiorganosiloxane,arylene, arylalkylene, and alkylarylene. A combination can be, forexample, an arylalkylene bonded to an alkylene (e.g.,alkylene-arylene-alkylene). In one example of analkylene-arylene-alkylene combination, the arylene is phenylene and eachalkylene has 1 to 10, 1 to 6, or 1 to 4 carbon atoms.

In some embodiments, the polydiorganosiloxane polyamide is apolydiorganosiloxane polyoxamide. The polydiorganosiloxane polyoxamidetends to be free of groups having a formula—B—(CO)—NH—where B is an alkylene.

All of the carbonylamino groups along the backbone of the copolymericmaterial typically are part of an oxalylamino group (i.e., the—(CO)—(CO)—NH— group), and B is a bond. That is, any carbonyl groupalong the backbone of the copolymeric material is bonded to anothercarbonyl group and is part of an oxalyl group. More specifically, thepolydiorganosiloxane polyoxamide has a plurality of aminoxalylaminogroups.

The polydiorganosiloxane polyamide is a block copolymer and can be anelastomeric material. Unlike many of the known polydiorganosiloxanepolyamides that are generally formulated as brittle solids or hardplastics, the polydiorganosiloxane polyamides can be formulated toinclude greater than 50 weight percent polydiorganosiloxane segmentsbased on the weight of the copolymer. The weight percent of thediorganosiloxane in the polydiorganosiloxane polyamides can be increasedby using higher molecular weight polydiorganosiloxanes segments toprovide greater than 60 weight percent, greater than 70 weight percent,greater than 80 weight percent, greater than 90 weight percent, greaterthan 95 weight percent, or greater than 98 weight percent of thepolydiorganosiloxane segments in the polydiorganosiloxane polyamides.Higher amounts of the polydiorganosiloxane can be used to prepareelastomeric materials with lower modulus while maintaining reasonablestrength.

Some of the polydiorganosiloxane polyamides can be heated to atemperature up to 200° C., up to 225° C., up to 250° C., up to 275° C.,or up to 300° C. without noticeable degradation of the material. Forexample, when heated in a thermogravimetric analyzer in the presence ofair, the copolymers often have less than a 10 percent weight loss whenscanned at a rate 50° C. per minute in the range of 20° C. to 350° C.Additionally, the copolymers can often be heated at a temperature suchas 250° C. for 1 hour in air without apparent degradation as determinedby no detectable loss of mechanical strength upon cooling. The linearblock copolymers having repeat units of Formula I can be prepared, forexample by reaction of at least one polydiorganosiloxane-containingprecursor with at least one diamine as described in U.S. Pat. No.7,371,464; incorporated herein by reference.

The diamines are sometimes classified as organic diamines orpolydiorganosiloxane diamines with the organic diamines including, forexample, those selected from alkylene diamines, heteroalkylene diamines(such as polyoxyalkylene diamines), arylene diamines, aralkylenediamines, or alkylene-aralkylene diamines. The diamine has only twoamino groups so that the resulting polydiorganosiloxane polyoxamides arelinear block copolymers that are often elastomeric, hot melt processable(e.g., the copolymers can be processed at elevated temperatures such asup to 250° C. or higher without apparent degradation of thecomposition), and soluble in some common organic solvents. The someembodiments, the diamine is free of a polyamine having more than twoprimary or secondary amino groups. Tertiary amines that do not reactwith the polydiorganosiloxane-containing precursor of can also bepresent. Additionally, the diamines utilized in the reaction are free ofany carbonylamino group. That is, the diamine is not an amide.

Preferred alkylene diamines (i.e., G is a alkylene) include, but are notlimited to, ethylene diamine, propylene diamine, butylene diamine,hexamethylene diamine, 2-methylpentamethylene 1,5-diamine (i.e.,commercially available from DuPont, Wilmington, Del. under the tradedesignation DYTEK A), 1,3-pentane diamine (commercially available fromDuPont under the trade designation DYTEK EP), 1,4-cyclohexane diamine,1,2-cyclohexane diamine (commercially available from DuPont under thetrade designation DHC-99), 4,4′-bis(aminocyclohexyl)methane, and3-aminomethyl-3,5,5-trimethylcyclohexylamine.

The polydiorganosiloxane polyoxamide copolymer can be produced using aplurality of polydiorganosiloxane precursors, a plurality of diamines,or a combination thereof. A plurality of precursors having differentaverage molecular weights can be combined under reaction conditions witha single diamine or with multiple diamines. For example, the precursorof may include a mixture of materials with different values of n,different values of p, or different values of both n and p. The multiplediamines can include, for example, a first diamine that is an organicdiamine and a second diamine that is a polydiorganosiloxane diamine.Likewise, a single precursor can be combined under reaction conditionswith multiple diamines.

Any suitable reactor or process can be used to prepare thepolydiorganosiloxane polyamide copolymer material. The reaction can beconducted using a batch process, semi-batch process, or a continuousprocess. Exemplary batch processes can be conducted in a reaction vesselequipped with a mechanical stirrer such as a Brabender mixer, providedthe product of the reaction is in a molten state has a sufficiently lowviscosity to be drained from the reactor. Exemplary semi-batch processcan be conducted in a continuously stirred tube, tank, or fluidized bed.Exemplary continuous processes can be conducted in a single screw ortwin screw extruder such as a wiped surface counter-rotating orco-rotating twin screw extruder.

The polydiorganosiloxane-containing precursor can be prepared by anyknown method. In some embodiments, this precursor is prepared accordingto the following reaction scheme, as described in previously cited U.S.Pat. No. 7,371,464 (Sherman et al.).

The polydiorganosiloxane diamine can be prepared by any known method andcan have any suitable molecular weight.

Further details on suitable polydiorganosiloxane polyamides (includingpolydiorganosiloxane diamines and particularly polydiorganosiloxanepolyoxamide) may be found, for example, among U.S. Pat. No. 8,586,668(Leir et al), U.S. Pat. No. 5,214,119 (Leir et al.), U.S. Pat. No.5,461,134 (Leir et al.), U.S. Pat. No. 5,512,650 (Leir et al.), and U.S.Pat. No. 7,371,464 (Sherman et al.), as well as U.S. Pat. Nos. 7,705,101and 8,431,671 (Sherman et al.). Some polydiorganosiloxane diamines arecommercially available, for example, from Shin Etsu Silicones ofAmerica, Inc., Torrance, Calif. and from Gelest Inc., Morrisville, Pa.

Other examples of suitable silicone elastomers includepolydiorganosiloxane polyuria. copolymers and blends thereof, such asthose described in U.S. Pat. Nos. 5,461,134 and 6,007,914 (Joseph etal.). Silicone-polyurethane copolymers (SPU) useful as film-formingpolymers in the compositions and methods according to the presentdisclosure include block copolymers comprising silicone blocks andsecondblocks derived from a multifunctional isocyanate. At points hereinthe term silicone-polyurea may be used interchangeable withsilicone-polyurethane. Useful silicone polyurea block copolymers aredisclosed in, e.g., U.S. Pat. Nos. 5,512,650, 5,214,119, and 5,461,134,and 6,569,521, 6,664,359 (Melancon et al.) as well as InternationalPublication Nos. WO 96/35458, WO 98/17726, WO 96/34028, WO 96/34030 andWO 97/40103.

Blocks derived from an isocyanate may have two functional groups (e.g.,—NHCONH— or —NHC(O)O—) attached to a divalent organic radical (such asalkyl groups, cycloalkyl groups, and aryl groups, containing from 1 to30 carbon atoms). Examples of useful diisocyanate compounds from whichsecond blocks may be derived are ethylene diisocyanate, 1,6-hexylenediisocyanate, 1,12-dodecylene diisocyanate, 4,4′-diphenylmethanediisocyanate, 3,3′-dimethoxy-4,4′-diphenylmethane diisocyanate,3,3′-dimethyl-4,4′-diphenylmethane diisocyanate, 4,4′-diphenyldiisocyanate, toluene-2,6,-diisocyanate, mixtures oftoluene-2,6-diisocyanate and toluene-2,4-diisocyanate, 1,4-cyclohexylenediisocyanate, 4,4′-dicyclohexylmethane diisocyanate,3,3′-diphenyl-4,4′-biphenylene diisocyanate, 4,4′-biphenylenediisocyanate, 2,4-diisocyanatodiphenylether, 2,4-dimethyl-1,3-phenylenediisocyanate, 4,4′-diphenylether diisocyanate, isophorone diisocyanate,and mixtures thereof.

Silicone blocks include those having the general formula (Si(R⁷)₂O—)wherein R⁷ is as defined above for any of the embodiments of R⁷ inFormula I. Non-limiting examples include dimethylsilicones,diethylsilicones, and diphenylsilicones.

Polydiorganosiloxane urethane-containing copolymers (a subset of theclass of SPU materials) useful in compositions of the present disclosurecontain soft polydiorganosiloxane units, hard polyisocyanate residueunits, terminal groups and optionally soft and/or hard organic polyamineresidue units. Some polydiorganosiloxane urea-containing copolymers arecommercially available under the trade designation “GENIOMER 140”available from Wacker Chemie AG, Germany. The polyisocyanate residue isthe polyisocyanate minus the —NCO groups, the organic polyamine residueis the organic polyamine minus the —NH groups, and the polyisocyanateresidue is connected to the polydiorganosiloxane units or organicpolyamine residues by urea linkages. The terminal groups may benon-functional groups or functional groups depending on the purpose ofthe polydiorganosiloxane urea segmented copolymer.

In some embodiments, the polydiorganosiloxane urethane containingcopolymers useful as polymer processing additives contain at least tworepeat units of Formula II

In this Formula II each R⁹ is a moiety that independently is an alkyl,cycloalkyl, aryl, perfluoroalkyl, or a perfluoroether group. In someembodiments of R⁹, alkyl has about 1 to 12 carbon atoms and may besubstituted with, for example, trifluoroalkyl, vinyl, a vinyl radical orhigher alkenyl represented by the formula —R¹⁰ (CH₂)_(a)CH═CH₂ whereinR¹⁰ is —(CH₂)_(b)— or —(CH₂)_(c)CH═CH— and a is 1, 2 or 3; b is 0, 3 or6; and c is 3, 4 or 5. In some embodiments of R⁹, cycloalkyl has about 6to 12 carbon atoms and may be substituted with one or more alkyl,fluoroalkyl, or vinyl groups. In some embodiments of R⁹, aryl has about6 to 20 carbon atoms and may be substituted with, for example, alkyl,cycloalkyl, fluoroalkyl and vinyl groups. In some embodiments of R⁹, theperfluoroalkyl group is as described in U.S. Pat. No. 5,028,679, whereinsuch description is incorporated herein by reference, and theperfluoroether-containing group is as described in U.S. Pat. Nos.4,900,474 and 5,118,775, wherein such descriptions are incorporatedherein by reference. In some embodiments, R⁹ is a fluorine-containinggroup is as described in U.S. Pat. No. 5,236,997, wherein suchdescription is incorporated herein by reference. In some embodiments, atleast 50% of the R⁹ moieties are methyl radicals with the balance beingmonovalent alkyl or substituted alkyl radicals having 1 to 12 carbonatoms, alkenylene radicals, phenyl radicals, or substituted phenylradicals. In Formula II, each Z′ is arylene, arylalkylene, alkylene, orcycloalkylene. In some embodiments of Z′, the arylene or arylalkylenehas from about 6 to 20 carbon atoms. In some embodiments of Z′, alkyleneor cycloalkylene radical has from about 6 to 20 carbon atoms. In someembodiments, Z′ is 2,6-tolylene, 4,4′-methylenediphenylene,3,3′-dimethoxy-4,4′-biphenylene, tetramethyl-m-xylylene,4,4′-methylenedicyclohexylene, 3,5,5-trimethyl-3-methylenecyclohexylene,1,6-hexamethylene, 1,4-cyclohexylene, 2,2,4-trimethylhexylene, ormixtures thereof. In Formula II, each Y′ is independently alkylene,arylalkylene, alkylarylene, or arylene. In some embodiments of Y′,alkylene has from 1 to 10 carbon atoms. In some embodiments of Y′, thearylalkylene, alkylarylene, or arylene has from 6 to 20 carbon atoms. InFormula II, each D is independently hydrogen, an alkyl radical having 1to 10 carbon atoms, phenyl, or a radical that completes a ring structureincluding B′ or Y′ to form a heterocycle. In Formula II, B is apolyvalent radical selected from the group consisting of alkylene,arylalkylene, alkylarylene, cycloalkylene, phenylene, polyalkylene oxide(e.g., polyethylene oxide, polypropylene oxide, polytetramethyleneoxide, and copolymers and mixtures thereof). In Formula II, “s” is anumber that is 0 to about 1000; “r” is a number that is equal to orgreater than 1; and “q” is a number that is about 5 or larger, in someembodiments about 15 to 2000, and in some embodiments about 30 to 1500.

In the use of polyisocyanates (Z′ is a radical having a functionalitygreater than 2) and polyamines (B′ is a radical having a functionalitygreater than 2), the structure of Formula II will be modified to reflectbranching at the polymer backbone. In the use of endcapping agents, thestructure of Formula II will be modified to reflect termination of thepolydiorganosiloxane urea chain.

The linear block copolymers having repeat units of Formula I andpolymdiorganolsiloxane urea containing polymers of Formula II can beprepared, for example, as discussed in U.S. Pat. No. 8,552,136 (Papp etal.).

Other examples of silicone containing polymers include those formed fromsilanols, silicone hydrides, siloxanes, epoxides, and (meth)acrylates.When the film-forming polymer is prepared from (meth)acrylate-functionalsiloxanes, the polymer is sometimes referred to as a siloxane(meth)acrylate. Additionally, other amphiphilic siloxy-containingpolymers have been reported as useful in gel compositions (U.S. Pat. No.7,795,326 (Salamone et al.)), wherein the hydrophobic siloxysilanemonomer is copolymerized with a hydrophilic nitrogen-containing monomer.Other siloxy-containing polymers include block copolymers ofpolydimethylsiloxane and polyurethane, and block copolymers ofpolydimethylsiloxane and poly(ethylene glycol). Still, other potentiallyviable film-forming polymers include block copolymers of polystyrene andethylene/butylene, block copolymers of polystyrene and polyisobutylene,block copolymers of polystyrene and polyisoprene, block copolymers ofpolystyrene and polybutadiene, block copolymers of polydimethylsiloxaneand polyurethanes, polymers of C4-C18 acrylates and methacrylates, butylrubber, polyisobutylene, and combinations thereof.

Another suitable siloxy-containing monomer for certain gel compositionsis based upon the siloxy monomer,3-methacryloyloxypropyltris(trimethylsiloxy)silane (TRIS). TRIS can beused in combination with both hydrophilic comonomers, such asN-isopropylacrylamide (NIPAM), or hydrophobic comonomers, such as methylmethacrylate, such that the resulting copolymers are soluble in avolatile solvent.

The film-forming polymer is typically present in quantities of at least5 wt. % and no greater than 30 wt. %, based on the total weight of thegel composition, or any amount within that range. In certainimplementations, it may be preferred that the film-forming polymer ispresent at a concentration of at least 12 wt. % and no greater than 25wt. %, based on the total weight of the gel composition.

A dried film cast form the gel composition may include an amount offilm-forming polymer in a range from 50 wt. % to 70 or 75 wt. % relativeto a total weight of the dried film, or any amount within that range.

Alternatively, gel compositions may feature polymerizable cyanoacrylatemonomers as the primary film-forming polymer. Cyanoacrylate monomersthat may be used include readily polymerizable alpha-cyanoacrylates,including alkyl cyanoacrylates, aryl cyanoacrylates, alkoxyalkylcyanoacrylates, such as butyl cyanoacrylate and n-butyl cyanoacrylate inparticular, octyl cyanoacrylate and 2-octyl cyanoacrylate in particular,ethyl cyanoacrylate, methyl cyanoacrylate, n-dodecyl cyanoacrylate,phenyl 2-cyanoacrylate, methoxyethyl 2-cyanoacrylate, and the like. Thecomposition may be composed of one or more polymerizable cyanoacrylatemonomers. Film-forming cyanoacrylates are as discussed in U.S. Pat. No.6,183,593 (Narang et al.) and U.S. Pat. No. 6,143,805 (Hickey et al.).Polymerizable cyanoacrylate esters in particular are described in U.S.Publication No. 2008/0152614 (Dunshee). Further cyanoacrylatecompositions are also disclosed by U.S. Pat. No. 5,480,935 (Greff etal.).

Tackifier

Tackifiers, such as silicate tackifying resins can be added to thefilm-forming polymer to provide or enhance the adhesive properties ofthe composition. The silicate tackifying resin can influence thephysical properties of the resulting gel composition. For example, assilicate tackifying resin content is increased, the glassy to rubberytransition of the gel composition occurs at increasingly highertemperatures. In some exemplary gel compositions, a plurality ofsilicate tackifying resins can be used to achieve desired performance.Suitable silicate tackifying resins include those resins composed of thefollowing structural units M (i.e., monovalent R′₃SiO_(1/2) units), D(i.e., divalent R′₂SiO_(2/2) units), T (i.e., trivalent R′SiO_(3/2)units), and Q (i.e., quaternary SiO_(4/2) units), and combinationsthereof. Typical exemplary silicate resins include MQ silicatetackifying resins, MQD silicate tackifying resins, and MQT silicatetackifying resins. These silicate tackifying resins usually have anumber average molecular weight in the range of 100 to 50,000 or in therange of 500 to 15,000 and generally have methyl R′ groups.

Such resins are described in, for example, Encyclopedia of PolymerScience and Engineering, vol. 15, John Wiley & Sons, New York, (1989),pp. 265-270, and U.S. Pat. No. 2,676,182 (Daudt et al.), U.S. Pat. No.3,627,851 (Brady), U.S. Pat. No. 3,772,247 (Flannigan), and U.S. Pat.No. 5,248,739 (Schmidt et al.). Other examples are disclosed in U.S.Pat. No. 5,082,706 (Tangney). The above-described resins are generallyprepared in solvent. Dried or solventless, M silicone tackifying resinscan be prepared, as described in U.S. Pat. No. 5,319,040 (Wengrovius etal.), U.S. Pat. No. 5,302,685 (Tsumura et al.), and U.S. Pat. No.4,935,484 (Wolfgruber et al.).

MQ silicate tackifying resins are particularly suitable for several gelcompositions of the present disclosure. MQ silicate tackifying resinsare copolymeric resins having R′₃SiO_(1/2) units (“M” units) andSiO_(4/2) units (“Q” units), where the M units are bonded to the Qunits, each of which is bonded to at least one other Q unit. Some of theSiO_(4/2) units (“Q” units) are bonded to hydroxyl radicals resulting inHOSiO_(3/2) units (“T° ^(H)” units), thereby accounting for thesilicon-bonded hydroxyl content of the silicate tackifying resin, andsome are bonded only to other SiO_(4/2) units.

Certain MQ silicate tackifying resins can be prepared by the silicahydrosol capping process described in U.S. Pat. No. 2,676,182 (Daudt etal.) as modified according to U.S. Pat. No. 3,627,851 (Brady), and U.S.Pat. No. 3,772,247 (Flannigan). These modified processes often includelimiting the concentration of the sodium silicate solution, and/or thesilicon-to-sodium ratio in the sodium silicate, and/or the time beforecapping the neutralized sodium silicate solution to generally lowervalues than those disclosed by Daudt et al. The neutralized silicahydrosol is often stabilized with an alcohol, such as 2-propanol, andcapped with R₃SiO_(1/2) siloxane units as soon as possible after beingneutralized. The level of silicon bonded hydroxyl groups (i.e., silanol)on the MQ resin may be reduced to no greater than 1.5 weight percent, nogreater than 1.2 weight percent, no greater than 1.0 weight percent, orno greater than 0.8 weight percent based on the weight of the silicatetackifying resin. This may be accomplished, for example, by reactinghexamethyldisilazane with the silicate tackifying resin. Such a reactionmay be catalyzed, for example, with trifluoroacetic acid. Alternatively,trimethylchlorosilane or trimethylsilylacetamide may be reacted with thesilicate tackifying resin, a catalyst not being necessary in this case.

The tackifier is typically added to the composition to at least 2 wt. %,in some embodiments at least 3 wt. %, in some embodiments at least 4 wt.%, in some embodiments at least 5 wt. %, based on the total weight ofthe gel composition. The tackifier is typically present in compositionat no greater than 20 wt. %, more preferably no greater than 15 wt. %,and most preferably no greater than 10 wt. % based on the total weightof the composition.

A dried film cast form the gel composition may include an amount oftackifier in a range from 5 wt. % to 25 or 30 wt. % relative to a totalweight of the dried film, or any amount within that range. In certainimplementations, films featuring less than 16 wt. % tackifier exhibitless adhesion to skin or other tissue than may be desired.

Coagulant

In certain advantageous embodiments, the gel composition includes acationic polymer that acts as a coagulant and repository for a certainvolume of exudate. This cationic polymer typically comprises acrosslinked, guanidinyl-containing polymer. The base polymer in theguanidinyl-containing polymer typically comprises a polyamine polymer;i.e., a polymer having primary or secondary amino groups that may bependent or catenary, i.e., in the polymer chain. The aminopolymerscontain primary or secondary amine groups and can be prepared by chaingrowth or step growth polymerization procedures with the correspondingmonomers. These monomers can also, if desired, be copolymerized withother monomers. The polymer can also be a synthesized or naturallyoccurring biopolymer. If any of these polymers, irrespective of source,do not contain primary or secondary amine groups, these functionalgroups can be added by the appropriate graft chemistry.

Useful aminopolymers are water soluble or water-dispersible. As usedherein, the term “water soluble” refers to a material that can bedissolved in water. The solubility is typically at least about 0.1 gramper milliliter of water. As used herein, the term “water dispersible”refers to a material that is not water soluble but that can beemulsified or suspended in water.

Examples of amino polymers suitable for use, which are prepared by chaingrowth polymerization include, but are not limited to: polyvinylamine,poly(N-methylvinylamine), polyallylamine, polyallylmethylamine,polydiallylamine, poly(-aminomethylstyrene), poly(4-aminostyrene),poly(acrylamide-co-methylaminopropylacrylamide), andpoly(acrylamide-co-aminoethylmethacrylate).

Examples of amino polymers suitable for use, which are prepared by stepgrowth polymerization include, but are not limited to: polyethylenimine,polypropylenimine, polylysine, polyaminoamides,polydimethylamine-epichlorohydrin-ethylenediamine, and any of a numberof polyaminosiloxanes, which can be built from monomers such asaminopropyltriethoxysilane,N-(2-aminoethyl)-3-aminopropyltrimethoxysilane,N-trimethoxysilylpropyl-N-methylamine, andbis(trimethoxysilylpropyl)amine.

Useful aminopolymers that have primary or secondary amino end groupsinclude, but are not limited to, those formed from polyamidoamine(PAMAM) and polypropylenimine: e.g., DAB-Am and PAMAM dendrimers (orhyperbranched polymers containing the amine or quaternary nitrogenfunctional group). Exemplary dendrimeric materials formed from PAMAM arecommercially available under the trade designation Starburst™ (PAMAM)dendrimer” (e.g., Generation 0 with 4 primary amino groups, Generation 1with 8 primary amino groups, Generation 2 with 16 primary amino groups,Generation 3 with 32 primary amino groups, and Generation 4 with 64primary amino groups) from Aldrich Chemical, Milwaukee, Wis. Dendrimericmaterials formed from polypropylenimine is commercially available underthe trade designation “DAB-AM” from Aldrich Chemical. For example,DAB-Am-4 is a generation 1 polypropylenimine tetraamine dendrimer with 4primary amino groups, DAB-Am-8 is a generation 2 polypropylenimineoctaamine dendrimer with 8 primary amino groups, DAB-Am-16 is ageneration 3 polypropylenimine hexadecaamine with 16 primary aminogroups, DAB-Am-32 is a generation 4 polypropylenimine dotriacontaaminedendrimer with 32 primary amino groups, and DAB-Am-64 is a generation 5polypropylenimine tetrahexacontaamine dendrimer with 64 primary aminogroups.

Examples of aminopolymers suitable for use, which are biopolymersinclude chitosan, and starch, where the latter is grafted with reagentssuch as methylaminoethylchloride.

Other categories of aminopolymers suitable for use includepolyacrylamide homo- or copolymers with amino monomers includingaminoalkyl(meth)acrylate, (meth)acrylamidoalkylamine, and diallylamine.Presently preferred aminopolymers include polyaminoamides,polyethyleneimine, polyvinylamine, polyallylamine, and polydiallylamine.

Suitable commercially available aminopolymers include, but are notlimited to, polyamidoamines such as ANQUAMINE™ 360, 401, 419, 456, and701 (Air Products and Chemicals, Allentown, Pa.); LUPASOL™polyethylenimine polymers such as FG, PR 8515, Waterfree, P, PS (BASFCorporation, Resselaer, N.Y.); polyethylenimine polymers such as CORCAT™P-600 (EIT Company, Lake Wylie, S.C.); polyoxyalkyleneamines such asJEFFAMINE.™ D-230, D-400, D-2000, HK-511 (XTJ-511), XTJ-510 (D-4000),XTJ-500 (ED-600), XTJ-502 (ED-2003), T-403, XTJ-509 (T-3000), and T-5000(Huntsman Corporation, Houston, Tex.); and polyamide resins such as theVERSAMID series of resins that are formed by reacting a dimerizedunsaturated fatty acid with alkylene diamines (Cognis Corporation,Cincinnati, Ohio).

The coagulant may be prepared by condensation of the polyamine polymerwith a guanylating agent. Known guanylating agents include: cyanamide;O-alkylisourea salts such as O-methylisourea sulfate, O-methylisoureahydrogen sulfate, O-methylisourea acetate, O-ethylisourea hydrogensulfate, and O-ethylisourea hydrochloride; chloroformamidinehydrochloride; 1-amidino-1,2,4-triazole hydrochloride;3,5-dimethylpyrazole-1-carboxamidine nitrate; pyrazole-1-carboxamidinehydrochloride; N-amidinopyrazole-1-carboxamidine hydrochloride; andcarbodiimides, such as dicyclohexylcarbodiimide,N-ethyl-N′-(3-dimethylaminopropyl)carbodiimide, anddiisopropylcarbodiimide. The polyamine polymer may also be acylated withguanidino-functional carboxylic acids such as guanidinoacetic acid and4-guanidinobutyric acid in the presence of activating agents such as EDC(N-[3-(dimethylamino)propyl]-3-ethylcarbodiimide hydrochloride), or EEDQ(2-ethoxy-1-ethoxycarbonyl-1,2-dihydroquinoline). Additionally, thecationic polymer may be prepared by alkylation with chloroacetone guanylhydrazone, as described in U.S. Pat. No. 5,712,027.

Reagents for the preparation of biguanide-functional polymers includesodium dicyanamide, dicyanodiamide and substituted cyanoguanidines suchas N³-p-chlorophenyl-N¹-cyanoguanidine, N³-phenyl-N¹-cyanoguanidine,N³-alpha-naphthyl-N¹-cyanoguanidine, N³-methyl-N¹-cyanoguanidine,N³,N³-dimethyl-N¹-cyanoguanidine, N³-(2-hydroxyethyl)-N¹-cyanoguanidine,and N³-butyl-N¹-cyanoguanidine. Alkylene- and arylenebiscyanoguanidinesmay be utilized to prepare biguanide functional polymers by chainextension reactions. The preparation of cyanoguanidines andbiscyanoguanidines is described in detail in Rose, F. L. and Swain, G.J. Chem Soc., 1956, pp. 4422-4425. Other useful guanylating reagents aredescribed by Alan R. Katritzky et al., Comprehensive Organic FunctionalGroup Transformation, Vol. 6, p. 640. Generally, such guanylationreagents are used in amounts sufficient to functionalize 0.5 to 100 molepercent, preferably 2.5 to 50 mole percent, of the available aminogroups of the aminopolymer.

The resulting polymer will have pendent or catenary guanidinyl groups ofthe formula III:

wherein

R² is a H, C₁-C₁₂ alkyl, C₅-C₁₂ (hetero)aryl, or a residue of thepolymer chain;

each R³ is independently H, C₁-C₁₂ alkyl, or C₅-C₁₂ (hetero)aryl,

each R⁴ is H, C₁-C₁₂ alkyl or alkylene, C₅-C₁₂ (hetero)aryl or(hetero)arylene, cyano, or —C(═NH)— N(R²)-Polymer, and

n is 1 or 2.

The guanidinyl-containing polymer can be crosslinked. Theamino-containing polymer can be crosslinked prior to reaction with theguanylating agent. Alternatively, the guanidinyl-containing polymer canbe crosslined by reaction of a crosslinker with remaining amino groupsfrom the amino-containing polymer precursor or with some of theguanidinyl groups. Suitable crosslinkers include amine-reactivecompounds such as bis- and polyaldehydes such as glutaraldehyde, bis-and polygylcidylethers such as butanedioldiglycidylether andethyleneglycoldiglycidylether, polycarboxylic acids and theirderivatives (e.g., acid chlorides), polyisocyanates, formaldehyde-basedcrosslinkers such as hydroxymethyl and alkoxymethyl functionalcrosslinkers, such as those derived from urea or melamine, andamine-reactive silanes, such as 3-glycidoxypropyltrimethoxysilane,3-glycidoxypropyltriethoxysilane, 5,6-epoxyhexyltrie thoxysilane,(p-chloromethyl)phenyltrimethoxysilane, chloromethyltriethoxysilane,3-isocyanatopropyltriethoxysilane, and3-thiocyanatopropyltriethoxysilane.

In other embodiments, the gel composition comprises a hemostatic agent,such as a polymerizable cyanoacrylate monomer. Other coagulants includemicrofibrillar collagen, chitosan, bone wax, ostene, oxidized celluloseand thrombin.

If included, coagulants are typically present in quantities of at least0.5 wt. % and no greater than 20 wt. %, based on the total weight of thegel composition, or any amount within that range. In certainimplementations, it may be preferred that the coagulant is present at aconcentration of at least 1 wt. % and no greater than 15 wt. %, and inyet other embodiments at least 1.5 wt. % and no greater than 10 wt. %,based on the total weight of the gel composition, or any amount withinthat range.

A dried film cast form the gel composition may include an amount ofcoagulant in a range from 5 wt. % to 30 or 35 wt. % relative to a totalweight of the dried film, or any amount within that range. In certaincircumstances and depending on particle size, the coagulant may remainin the film during treatment, at the surface thereof, may migrate intothe wound or target area to assist for localized coagulation, or somecombination thereof. The film can act, in these circumstances, as acoagulant delivery system to the underlying target area.

If a silicone containing film-forming polymer is used, a siliconesurfactant may be incorporated to assist in stabilizing the coagulant inthe gel composition. Silicone surfactants typically includepolydimethylsiloxane (PDMS) fluids and/or organomodified PDMS fluidssuch as siloxane polyether copolymers. One exemplary suitable PDMSsurfactant is a monocarboyxldecyl terminated polydimethylsiloxane,(available as MCR-B-12 from Gelest LTD, Kent, UK). Other suitable PDMSsurfactants include Abil Quat 3272, available from Evonik Goldschmidt,Germany. Another suitable surfactant isdimethoxymethylsilylpropyl-polyethylene Imine—50% in IPA, available fromGelest. In certain circumstances, the silicone surfactant can improveadhesion of the gel (and the resultant dried film) to tissue.

If included, silicone surfactants are typically present in quantities ofat least 0.1 wt. % and no greater than 15 wt. %, based on the totalweight of the gel composition. A dried film cast from the gelcomposition may include an amount of silicone surfactant in a range from1 wt. % to 15 or 20 wt. % relative to a total weight of the dried film,or any amount within that range.

In certain formulations that feature a guanidinyl-containing polymer asa coagulant, it can be useful to include a relatively small amount ofsilicone surfactant or none at all. In such compositions, the siliconesurfactant is present in quantities of no greater than 0.25 wt. %, basedon the total weight of the gel composition. Applicants have found someevidence that, in contrast to the expected stabilization, the inclusionof greater than 0.25 wt. % can (in certain circumstances) decrease thestability of the composition over an otherwise expected storage life.

Amine-Rich Adhesion Promoter

In lieu of or in addition to the coagulant and tackifier, the gelcompositions of the present disclosure may include an amine-richadhesion promoter. The amine-rich adhesion promoter can, in presentlypreferred circumstances, be an aminosilicone. Other suitable amine-richadhesion promoters include polymeric cationic ammonium compounds such aspolyhexamethylene biguanide (i.e., polyaminopropyl biguanide) andcertain of the aminopolymers described above that serve as the base forguanidynyl-containing coagulants.

Applicants have found that certain amine rich compounds promote skinadhesion without deleteriously affecting the rheology of the gelcomposition or the other properties of films formed from such gelcompositions. Furthermore, these adhesion promoters allow for improvedadhesion with less tackifier present in the gel composition, which canbe important for maintaining the integrity of a film formed on the skin.In particular, those compounds having an amine number greater than 25and a ratio of amine number to viscosity of less than 1.0 appear toprovide the desired skin adhesion (e.g., at least 25 g/inch) even in theabsence of coagulant, tackifier, or both. In the present disclosure,“amine number” represents the number of milliliters of 0.1N HCl neededto neutralize 10 g of the amine-rich adhesion promoter. Amine number ispreferably calculated according to the following equation:1/FGMW*times 100,000

*FGMW=functional group molecular weight of the amine groups

In some embodiments, the adhesion promoter has an amine number greaterthan 20, in some embodiments greater than 25, in some embodimentsgreater than 30, in some embodiments greater than 40, in someembodiments greater than 45, and in some embodiments greater than 50.Without wishing to be bound by theory, the amine content of the adhesionpromoter appears, among other parameters and characteristics of thepromoter, to be directly correlated with improved adhesion to skin.Accordingly, adhesion promoters suitable for use in the gel compositionsof the present advantageously typically include a greater number ofavailable amine groups and an attendant, larger amine number.

In some embodiments, the adhesion promoter has an amine number toviscosity ratio of less than 4, in some embodiments less than 2, in someembodiments less than 1, in some embodiments less than 0.5, in someembodiments less than 0.2, and in some embodiments less than 0.1.Without being bound by theory, adhesion promoters having both a highamine number and a high molecular weight (and thus a high viscosity),among other parameters, appear to be directly correlated with improvedadhesion of the gel compositions to skin.

As used herein “aminosilicone” means any amine functionalized silicone;i.e., a silicone containing at least one primary amine, secondary amine,tertiary amine, or a quaternary ammonium group. Typically, these aresilicones which have been chemically modified so that some of thependant groups along the backbone have been replaced with variousalkylamine groups (—R—NH₂). These amine groups can become positivelycharged in aqueous solutions because of their electron-donatingtendencies, yielding an inorganic, cationic polymer. Usefulaminosilicones are typically water soluble or water-dispersible.

Exemplary aminosilicones for use in embodiments of the presentdisclosure can be linear polymers, branched polymers, copolymers, andmixtures thereof. In some embodiments the copolymer is a blockcopolymer. In some embodiments, including those of presently preferredcompositions, the aminosilicone has one or more amine groups pendantfrom the polymer backbone. Examples of such embodiments are illustratedby compounds of formula IV with pendant mono-amines and compounds ofFormula VI with pendant di-amines, as shown herein below. In someembodiments the polymer has amine groups at one or more termini of thepolymer. Examples of such embodiments are illustrated by compounds ofFormula V, as shown herein below. Aminosilicones may further be selectedfrom the group comprising, aminodimethicones,trimethylsilylamodimethicones,aaminoethylaminopropylsiloxane-dimethylsloxane copolymers, and mixturesthereof.

In some embodiments, an aminosilicone has the structure of Formula IV:

wherein R is C1-12 (preferably C1-6) alkyl, the blocks bearing thesubscripts x and y may be randomly mixed, the total value of x is from10 to 5,000, for example 58 or 100 or 118, and the total value of y isfrom 2 to 20, preferably 2 to 11, for example 4 or 11. In someembodiments x is 58 and y is 4; x is 100 and y is 4; or x is 118 and yis 11. In some embodiments, R is a linear C₃H₆ group.

In some embodiments, one or more aminosilicones have the structure offormula V, which features terminal amine groups:

wherein x is from 5 to 5,000, and R and R′, which may be the same ordifferent, are each saturated, linear or branched alkyl groups of 1 to12 carbon atoms (in presently preferred circumstances, 1 to 6 carbonatoms), e.g., a linear C₃H₆ group.

In other embodiments the aminosilicone includes a branched diaminofunctional polydimethylsiloxane of formula VI:

wherein the blocks bearing the subscripts x and y may be randomly mixed,the total value of is from 5 to 5,000, the total value of y is from 1 to20, e.g., 8, and R and R′, which may be the same or different, are eachsaturated, linear or branched alkyl groups of 1 to 12 carbon atoms(preferably 1 to 6), e.g., R is a linear C₃H₆ group and R′ is a linearC₂H₄ group.

In some embodiments, the aminosilicone is selected from the groupcomprising GP-4 (a compound of formula IV wherein R=(CH₂)₃, x=58 andy=4, available for example from Genesee Polymers Corporation (“GPC”),Burton, Mich., USA, and having an amine number of about 90), GP-6 (acompound of formula IV, wherein R=(CH₂)₃, x=100 and y=4, available forexample from GPC and having an amine number of about 49), GP-316 (acompound of formula III wherein R=(CH₂)₃, R′=(CH₂)₂, x=400 and y=8,available for example from GPC and having an amine number of about 54),GP-581 (a compound of formula IV wherein R=(CH₂)₃, x=118 and y=11,available for example from GPC and having an amine number of about 110),GP-965 (a compound of formula V wherein R=R′=(CH₂)₃, x=10, available forexample from GPC and having an amine number of about 200), KF-861 (acompound of formula VI having an amine number of about 127, availablefor example from Shin-Etsu Silicones, Akron, Ohio), KF-864 (a compoundof formula IV having an amine number of about 26, available for examplefrom Shin-Etsu Silicones), KF-869 (a compound of formula VI having anamine number of about 54, available from Shin-Etsu Silicones), KF-393 (adiamino modified compound of formula IV having an amine number of about286, available from Shin-Etsu Silicones), KF-880 (a diamino modifiedcompound of formula IV having an amine number of about 56, availablefrom Shin-Etsu Silicones), KF-8004 (a diamino modified compound offormula IV having an amine number of about 67, available from Shin-EtsuSilicones), Silamine® AO EDA (a compound of formula VI wherein R=(CH₂)₃,R′=(CH₂)₂, having an amine number of about 230, available from SiltechCorporation, Toronto, Ontario, Canada), Silamine® D2 EDA (a compound offormula VI wherein R=(CH₂)₃, R′=(CH₂)₂, having an amine number of about170, available for example from Siltech Corporation), Silamine® D208 EDA(a compound of formula VI, wherein part of the dimethyl siloxanerepeating units are further substituted by polyether groups and whereinR=(CH₂)₃, R′=(CH₂)₂, the compound having an amine number of about 30,available from Siltech Corporation), commercial alternatives thereof(such as amine silicones from other suppliers, as will be appreciated bypersons skilled in the art), and mixtures thereof.

In presently preferred circumstances, the selected aminosilicone has oneor more di- or mono-amine groups pendant from the polymer backbone.

Other potential suitable aminosilicones include certain quaternarysilicones. One understands by “quaternary silicone” any siliconecomprising one or more quaternary ammonium groups. Compositions of thepresent invention can comprise at least one silicone quaternary compoundselected from silicone quaternium-12 (available, for example, as PECOSILCA-1240, a reaction product of cocamidopropyldimethylamine andDimethicone PEG-7 acetyl chloride, from Phoenix Chemical, Somerville,N.J.), silicone quaternium-8 (available, for example, as PECOSIL AD-3640silicone quaternium-19 (available, for example, as ZENESTER Q, afunctionalized cationic polymeric silicone polyester made from thereaction of a cationic dimethicone copolyol and a dimer acid, fromZenitech, Ontario, CA), silicone quaternium-22 (available as Abil T quat60), silicone quaternium-80 (available as Abil T Quat 3272), andmixtures thereof.

Particularly preferred quaternary silicones include those sold asPECOSIL AD-3640 and PECOSIL CA-1240, each having the formula:

Without wishing to be bound by theory, gel compositions of the presentdisclosure may require relatively more of a given quaternary silicone toachieve the same skin adhesion performance as a suitable aminosilicone,holding other components of the composition constant. Furthermore, suchcomposition may still benefit from the presence of a tackifier.

Suitable aminopolymers for use as adhesion promoters include the basepolymers in the guanidinyl-containing polymers described above,including polyaminoamides, polyethyleneimine, polyvinylamine,polyallylamine, and polydiallylamine. Presently preferred aminopolymersinclude polyethyleneimine. Polyethylenimine (PEI) is commerciallyavailable in several forms such as linear, branched, and dendrimeric.Linear PEI can be represented by Formula VIII, below:

wherein --- indicates continued linear polymeric ethylenimine-derivedunits or H. Linear PEIs are commercially available and/or can be madeaccording to known methods.

An exemplary branched PEI fragment can be represented by Formula IX,below:

wherein --- indicates continued linear and/or branched polymericethylenimine-derived units or H. As branching is typically more or lessrandom, branched PEIs typically contain many compounds of this generaltype as a mixture. Branched PEI can be synthesized by the ring openingpolymerization of aziridine. Branched PEIs are commercially availableand/or can be made according to known methods.

Dendrimeric PEI is a special case of a branched PEI. An exemplary(generation 4) dendrimeric PEI is represented by Formula X, below:

In this case, the PEI contains only primary and tertiary amino groups.Dendrimeric PEIs are commercially available and/or can be made accordingto known methods.

In another embodiment, the amine-rich adhesion promoter may comprise,consist essentially of, or even consist of, a silylated aminopolymer.The silylated aminopolymer may be a polyamine having at least one silaneor alkoxysilane moiety attached anywhere within the polyamine. Silylatedpolyamines can be prepared, for example, by reaction of anamine-reactive organosilane coupling agent with at least some of theprimary amines present in an aminopolymer, such as branched PEI.Exemplary amine-reactive organosilane coupling agents include:3-isocyanatopropyltriethoxysilane; 3-isocyanatopropyltrimethoxysilane;2-isocyanatoethyltriethoxysilane; 2-isocyanatoethyltrimethoxysilane;3-acryloxypropyltriethoxysilane; 3-acryloxypropyltrimethoxysilane;2-acryloxyethyltriethoxysilane; 2-acryloxyethyltrimethoxysilane;3-glycidoxypropyltriethoxysilane; 3-glycidoxypropyltrimethoxysilane;2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; and2-(3,4-epoxycyclohexyl)ethyltriethoxysilane. The silylated polyamine maybe, but is not limited to, silylated polyethylenimine (SPEIm), silylatedpolyvinylpyridine, silylated polydimehtylaminoethylmethacrylate,silyated polyvinylamine, silylated polyallylamine (PAAm) or combinationsthereof. In an illustrative embodiment, the silylated polyaminecomprises or is trimethoxysilylpropyl modified polyethylenimine.

If included in lieu of or in addition to a coagulant, amine-richadhesion promotors are typically present in quantities of at least 0.5wt. % and no greater than 20 wt. %, based on the total weight of the gelcomposition, or any amount within that range. In certainimplementations, it may be preferred that the amine-rich adhesionpromoter is present at a concentration of at least 1 wt. % and nogreater than 15 wt. %, and in yet other embodiments at least 1.5 wt. %and no greater than 10 wt. %, based on the total weight of the gelcomposition, or any amount within that range.

A dried film cast form the gel composition may include an amount ofamine-rich adhesion promoter in a range from 5 wt. % to 30 or 35 wt. %relative to a total weight of the dried film, or any amount within thatrange.

If included in a gel composition in lieu of both a coagulant and atackifier, the adhesion promoter is typically added to the compositionto at least 2.5 wt. %, in some embodiments at least 4 wt. %, in someembodiments at least 5 wt. %, based on the total weight of the gelcomposition. In such compositions, the amine-rich adhesion promoter istypically present in composition at no greater than 35 wt. %, morepreferably no greater than 25 wt. %, and most preferably no greater than20 wt. % based on the total weight of the composition.

A dried film cast form the gel composition lacking coagulant ortackifier may include an amount of amine-rich adhesion promoter in arange from 10 wt. % to 55 or 60 wt. % relative to a total weight of thedried film, or any amount within that range.

Solvent

The coating gel composition further comprises a volatile solvent. In oneembodiment, the volatile solvent is selected from the group consistingof volatile linear and cyclic siloxanes, volatile polydimethylsiloxanes,isooctane, octane, and combinations thereof. The solvent is typically atleast 40 wt. % of the total gel composition. As the composition may beapplied to tissue, the solvent is desirably volatile and non-stinging.In one embodiment, at least 60 wt. % of the total composition is thesolvent. In yet other embodiments, the solvent is present in at least 70wt. % of the total composition.

The solvent system for the gel compositions of the present disclosurecan be a non-polar, volatile solvent such as isooctane. Other exemplaryvolatile solvent systems include a linear siloxane or a cyclic siloxane,such as hexamethyldisiloxane (HMD S), octamethylcyclotetrasiloxane,decamethylcyclopentasiloxane, and octamethyltrisiloxane, or a linear,branched or cyclic alkane, such as propane, isobutane, liquid butane(e.g., under pressure), pentane, hexane, heptane, octane, petroleumdistillates, cyclohexane, fluorocarbons, such astrichloromonofluoromethane, dichlorodifluoromethane,dichlorotetrafluoroethane, tetrafluoroethane, heptafluoropropane,1,1-difluoroethane, pentafluoropropane, perfluoroheptane,perfluoromethylcyclohexane, 1,1,1,2,-tetrafluoroethane,1,1,1,2,3,3,3-heptafluoropropane, chlorofluorocarbons, in addition toliquid carbon dioxide, and combinations thereof. As used herein,“volatile” has its standard meaning, that is, it can evaporate rapidlyat normal temperatures and pressure. For example, a solvent can bevolatile if one metric drop ( 1/20 mL, 50 mu L) of the solvent willevaporate completely between 20-25° C. within 5 minutes, or within 4minutes, or within 3 minutes, or within 2 minutes, or within 1 minute,or within 30 sec, or within 15 sec.

The use of non-polar, volatile solvents, alone or in combination, as theprimary liquid phase of the gel composition can provide a desirablebalance between fast drying and reduced skin irritation duringapplication. In presently preferred implementations, the solvent is oneof HMDS and isooctane. Other, more polar solvents such as ethanol,isopropanol, glycerin, N-methylpyrrolidone, and N,N-dimethylacetamidecan be used in other implementations, where a non-stinging gelcomposition is either unnecessary or undesirable. Numerous aproticsolvents have utility including acetates such as methyl and ethylacetate, propylene glycol diacetate, volatile ketones such as acetoneand methyl ethyl ketone, volatile ethers such as diethyl ether, ethylpropyl ether, dipropyl ether and dipropylene glycol dimethyl ether,volatile fluorocarbons, such as pentafluoropropane, perfluoroheptane,perfluoromethylcyclohexane and the like; or a volatile gas, such ascarbon dioxide, can also be employed, each with varying degrees of userdiscomfort.

In some implementations, water may be included in a solvent system,which can be useful in solublizing certain active agents and hemostats.In certain implementations, a relatively small amount of water ispresent in the gel composition, such as at least 0.1 wt. %, based on thetotal weight of the composition. In other embodiments, the water contentis at least 60 wt. %, based on the total weight of the composition,though such composition may require longer dry times than presentlydesired. Certain solvent systems including water are exemplified in U.S.Pat. No. 7,651,990 (Asmus), and U.S. Pat. No. 8,338,491 (Asmus et al.).

Additives

The gel compositions of the present disclosure may include filler.Examples of suitable fillers are naturally occurring or syntheticmaterials including, but not limited to: quartz (i.e., silica, SiO₂);nitrides (e.g., silicon nitride); glasses and fillers derived from, forexample, Zr, Sr, Ce, Sb, Sn, Ba, Zn, and Al; feldspar; borosilicateglass; kaolin (china clay); talc; zirconia; titania; and submicronsilica particles (e.g., pyrogenic silicas such as those available underthe trade designations AEROSIL, including “OX 50,” “130,” “150” and“200” silicas from Degussa Corp., Akron, Ohio and CAB-O-SIL M5 andTS-720 silica from Cabot Corp., Tuscola, Ill.). Organic fillers madefrom polymeric materials are also possible, such as disclosed in PCTPublication No. WO09/045752 (Kalgutkar et al.).

Clay materials suitable for use in compositions, methods, and articlesof the present disclosure can include those in the geological classes ofthe smectites, the kaolins, the illites, the chlorites, the serpentines,the attapulgites, the palygorskites, the vermiculites, the glauconites,the sepiolites, and the mixed layer clays. Smectites, for example, caninclude montmorillonite, bentonite, pyrophyllite, hectorite, saponite,sauconite, nontronite, talc, beidellite, and volchonskoite. Kaolins, forexample, can include kaolinite, dickite, nacrite, antigorite, anauxite,halloysite, indellite and chrysotile. Illites, for example, includebravaisite, muscovite, paragonite, phlogopite and biotite. Chlorites,for example, can include corrensite, penninite, donbassite, sudoite,pennine and clinochlore. Mixed layer clays, for example, can includeallevardite and vermiculitebiotite. Variants and isomorphicsubstitutions of these layered clay minerals offer unique applications.

A typical gel composition of the present disclosure includes at leastone of kaolin and fumed silica. In certain implementations, theinclusion of fumed silica can enhance the ability of the gel compositionto form a substantially level film surface and ease of removing thedried film by peel. Appropriate amounts of filler will be familiar tothose skilled in the art, and will depend upon numerous factorsincluding, for example, the polymer(s) utilized, the type of filler, andthe intended treatment area(s) of the gel composition. Typically, fillerwill be added at a level of about 1% to about 20% by weight (preferably,about 3% to about 15% by weight), based upon the total weight of the gelcomposition, or any amount within that range. A dried film cast form thegel composition may include an amount of filler in a range from 0.1 wt.% to 30 wt. % relative to a total weight of the dried film, or anyamount within that range.

If biocidal (or in certain implementations bacteriostatic) propertiesare desired, antiseptic and/or antibiotic agents may be suspended orotherwise dispersed in the gel composition. In some implementations, theantiseptic is a cationic antimicrobial agent including an effectiveamount of one or more antimicrobial agents selected from the groupconsisting of biguanides and bisbiguanides such as chlorhexidine,alexidine, and their various salts including but not limited to thedigluconate, diacetate, dimethosulfate, and dilactate salts, as well ascombinations thereof; polymeric cationic ammonium compounds such aspolyhexamethylenebiguanide salts; small molecule quaternary ammoniumcompounds such as benzalkonium halides; cationic antimicrobial dyes; andcompatible combinations thereof.

Particularly useful cationic antimicrobial agents include benzalkoniumchloride, chlorhexidine gluconate, octenidine dihydrochloride, cetylpyridinium chloride, cetrimonium bromide, benzethonium chloride,polyhexamethylene biguanide salt, methylene blue, toluidiene blue,cationic dyes and compatible combinations thereof. Additional detailsregarding exemplary cationic antimicrobial agents may be found inInternational Publication No. WO2014/008264 (Parthasarathy et al.)

The antiseptic agent is typically added to the composition at aconcentration of at least 0.01 wt. %, in some embodiments at least 0.05wt. %, in some embodiments at least 0.1 wt. %, in some embodiments atleast 0.2 wt. %, in some embodiments at least 0.5 wt. %, in otherembodiments at least 0.6 wt. %, in yet other embodiments at least 1.0wt. % and in yet other implementations at least 1.5 wt. %, in some casesexceeding 2 wt. %., based on the total weight of the gel composition.Preferably, the composition comprises not greater than 10 wt. %, morepreferably no greater than 8 wt. %, and most preferably no greater than5 wt. %. A potential range for antiseptic agent concentration to enhanceactive kill is at least 0.1 wt. % and no greater than 1.0 wt. %, basedon the total weight of the composition. A dried film cast form the gelcomposition may include an amount of antiseptic agent in a range from0.1 wt. % to 4 wt. % relative to a total weight of the dried film, orany amount within that range. It should be appreciated that the aboveconcentrations relate to the total amount of cationic agent in thecomposition, even if a plurality of cationic antimicrobial agents areused.

In certain embodiments, the gel composition can have a synergisticantimicrobial effective amount of an antiseptic surfactants,particularly straight chain 1,2-alkanediols having a chain length in therange of 5 to 10 carbon atoms. Such 1,2-alkanediols include,1,2-pentanediol, 1,2-hexanediol, 1,2-heptanediol, 1,2-octanediol,1,2-nonanediol, and 1,2-decanediol, and combinations thereof. Oneexemplary suitable 1,2-octanediol composition includes3[(2-ethylhexyl)oxy]-1,2-propanediol, and is sold as SENSIVA SC-10 bySchülke&Mayr GmbH, Germany. Without wishing to be bound by theory, theinclusion of straight chain 1,2-alkanediols can reduce the tendency ofcertain cationic antimicrobial agents (e.g., benzethonium chloride) tocrystallize in a dried film. By preventing or otherwise reducing thetendency to crystallize, the straight chain 1,2-alkanediols can prolongthe availability of the antimicrobial agent, in that the active killtime is enhanced. A dried film cast form the gel composition may includean amount of antiseptic surfactant in a range from 0.5 wt. % to 2 wt. %relative to a total weight of the dried film, or any amount within thatrange.

A particularly cogent property of certain gel compositions including anantiseptic agent is the ability to reduce the bacterial load on tissue,particularly skin (e.g., to kill the natural skin flora). In certainembodiments, the dried film achieves at least 1 log reduction of atarget microorganism in 2 hours when evaluated by the AntimicrobialEfficacy Test described below. In more desirable embodiments, thecompositions achieve a 2 log reduction. In even more desirableembodiments, the compositions achieve a 3 log reduction. In certainembodiments, the target organisms comprise Pseudomonas aeruginosa,Staphylococcus aureus, Escherichia coli, and methicillin-resistantStaphylococcus aureus. In certain embodiments, residual antimicrobialefficacy is provided to any surface formed from the dried gelcomposition. In certain embodiments, the dried film provides an activekill for an extended period of time during the life of the film.

Other anti-infective agents, such as nano-silver particles and silversulfadiazine, may also be added to gel compositions of the presentinvention. Such anti-infective agents can be added as suspended solidsto the coating polymer in the volatile solvent. Topical antibiotics suchas neomycin, polymyxin B, and bacitracin can also be included. Othersolid biologically active materials, such as anti-itch agents, such aschamomile, Eucalyptus, camphor, menthol, zinc oxide, talc, and calamine,anti-inflammatory agents, such as corticosteroids, antifungal agents,such as terbinafine hydrochloride and miconazole nitrate, andnon-steriodal anti-inflammatory agents, such as ibuprofen, can be addedin like fashion. Essential oils can also be added as flavoring agents,aromatic agents, or antimicrobial agents, including thymol, menthol,sandalwood, cinnamon, jasmine, lavender, pine, lemon, rose, Eucalyptus,clove, orange, mint, spearmint, peppermint, lemongrass, bergamot,citronella, cypress, nutmeg, spruce, tea tree, wintergreen, vanilla, andthe like. After evaporation of the volatile, solvent, the dried film maycontain entrapped active biological or pharmaceutical ingredients forcontrolled release to a biological surface.

Other exemplary antimicrobials agents useful as antiseptics includephenolic antiseptics such as parachlorometaxylenol (PCMX), triclosan,hexachlorophene, and others disclosed in U.S. Pat. No. 8,198,326(Scholz); fatty acid monoesters of glycerin and propylene glycol such asglycerol monolaurate, glycerol monocaprylate, glycerol monocaprate,propylene glycol monolaurate, propylene glycol monocaprylate, propyleneglycol moncaprate, C₈-C₁₂ alkyl monoethers of glycerin and propyleneglycol such as 2-ethylhexyl glycerin ether (available from SchuelkeMayr, Norderstedt, Germany, under the trade designation “SENSIVA SC50”), natural oil antiseptics; C₆-C₁₂ alkyl and aryl carboxylic acids;quaternary silanes, silver, silver salts such as silver chloride, silveroxide silver sulfadiazine, copper, copper salts, and combinationsthereof.

Other examples of actives agents (or drugs) that can be incorporatedinto the gel compositions of the present disclosure are those capable oflocal or systemic effect when administered to the skin. Some examplesinclude buprenorphine, clonidine, diclofenac, estradiol, granisetron,isosorbide dinitrate, levonorgestrel, lidocaine, methylphenidate,nicotine, nitroglycerine, oxybutynin, rivastigmine, rotigotine,scopolamine, selegiline, testosterone, tulobuterol, and fentanyl. Otherexamples include, but are not limited to, antiinflammatory drugs, bothsteroidal (e.g., hydrocortisone, prednisolone, triamcinolone) andnonsteroidal (e.g., naproxen, piroxicam); bacteriostatic agents (e.g.,chlorhexidine, hexylresorcinol); antibacterials (e.g., penicillins suchas penicillin V, cephalosporins such as cephalexin, erythromycin,tetracycline, gentamycin, sulfathiazole, nitrofurantoin, and quinolonessuch as norfloxacin, flumequine, and ibafloxacin); antiprotazoals (e.g.,metronidazole); antifungals (e.g., nystatin); coronary vasodilators;calcium channel blockers (e.g., nifedipine, diltiazem); bronchodilators(e.g., theophylline, pirbuterol, salmeterol, isoproterenol); enzymeinhibitors such as collagenase inhibitors, protease inhibitors,acetylcholinesterase inhibitors (e.g., donepezil), elastase inhibitors,lipoxygenase inhibitors (e.g., A64077), and angiotensin convertingenzyme inhibitors (e.g., captopril, lisinopril); other antihypertensives(e.g., propranolol); leukotriene antagonists (e.g., ICI204,219);anti-ulceratives such as H2 antagonists; steroidal hormones (e.g.,progesterone); antivirals and/or immunomodulators (e.g.,1-isobutyl-1H-imidazo[4,5-c]quinolin-4-amine,1-(2-hydroxy-2-methylpropyl)-1H-imidazo[4,5-c]quinolin-4-amine,N-[4-(4-amino-2-ethyl-1H-imidazo[4,5-c]quinolin-1-yl)butyl]methanesulfonamide,and acyclovir); local anesthetics (e.g., benzocaine, propofol,tetracaine, prilocaine); cardiotonics (e.g., digitalis, digoxin);antitussives (e.g., codeine, dextromethorphan); antihistamines (e.g.,diphenhydramine, chlorpheniramine, terfenadine); narcotic analgesics(e.g., morphine, fentanyl citrate, sufentanil, hydromorphonehydrochloride); peptide hormones (e.g., human or animal growth hormones,LHRH, parathyroid hormones); cardioactive products such asatriopeptides; antidiabetic agents (e.g., insulin, exanatide); enzymes(e.g., anti-plaque enzymes, lysozyme, dextranase); antinauseants;anticonvulsants (e.g., carbamazine); immunosuppressives (e.g.,cyclosporine); psychotherapeutics (e.g., diazepam); sedatives (e.g.,phenobarbital); anticoagulants (e.g., heparin, enoxaparin sodium);analgesics (e.g., acetaminophen, camphor, lidocaine, and others listedin 21 C.F.R 348.10, Analgesic, anesthetic, and antiprunitic activeingredients (Apr. 1, 2012)); antimigraine agents (e.g., ergotamine,melatonin, sumatriptan, zolmitriptan); antiarrhythmic agents (e.g.,flecainide); antiemetics (e.g., metaclopromide, ondansetron, granisetronhydrochloride); anticancer agents (e.g., methotrexate); neurologicagents such as anxiolytic drugs; anti-obesity agents; dopamine agonists(e.g., apomorphine); GnRH agonists (e.g., leuprolide, goserelin,nafarelin); fertility hormones (e.g., hCG, hMG, urofollitropin);interferons (e.g., interferon-alpha, interferon-beta, interferon-gamma,pegylated interferon-alpha); and the like, as well as pharmaceuticallyacceptable salts and esters thereof.

The compositions may further contain fibrous reinforcement and colorantssuch as dyes, pigments, and pigment dyes. Examples of suitable fibrousreinforcement include PGA microfibrils, collagen microfibrils, andothers as described in U.S. Pat. No. 6,183,593. Examples of suitablecolorants as described in U.S. Pat. No. 5,981,621 include1-hydroxy-4-[4-methylphenylamino]-9,10-anthracenedione (FD&C violet No.2); disodium salt of6-hydroxy-5-[(4-sulfophenyl)oxo]-2-naphthalenesulfonic acid (FD&C YellowNo. 6);9-(o-carboxyphenyl)-6-hydroxy-2,4,5,7-tetraiodo-3H-xanthen-3-one,disodium salt, monohydrate (FD&C Red No. 3); and the like.

The use of florescent dyes and pigments can also be beneficial inenabling the coating to be viewed under black-light. The coating couldbe substantially clear and transparent under normal lighting so the sitecan be easily viewed and inspected for changes in the skin. As a meansof ensuring the coating is intact and covering the desired area, thesite can be inspected by the use of a backlight wand or flashlight whichreveals the coating by its florescence. A particularly usefulhydrocarbon soluble fluorescing dye is2,5-bis(5-tert-butyl-2-benzoxazolyl) 1 thiophene. Fluorescing dyes, suchas rhodamine, may also be bound to cationic polymers and incorporated aspart of the coagulant.

Kits

The gel compositions of the present disclosure may advantageously beprovided in a kit. The kit may contain an applicator, a wound cleaningsolution, and an absorbent material. In some implementations, the gelcomposition is arranged in the kit in a vial or other rupturable packageseparate from the applicator. In other implementations, the applicatoris pre-loaded with the gel composition (e.g., in a delivery reservoir).

Methods of Application and Removal

A treatment protocol may involve skin preparation prior to applying thegel compositions of the present disclosure. The target site ispreferably dried, e.g., blotted dry, and then a lightly adherentpolymeric film is formed over this site by applying the gel composition.

Sufficient amounts of the composition are employed to cover (i.e., coat)the entire target site with a layer of the gel composition. It istypically preferred that the resultant dried film have a thickness fromabout 4 to about 15 mills. The resultant film typically covers at leastthe entire area of the wound or other target site, but may not underother circumstances. If necessary, excess gel can be removed with a wipeor tissue paper before drying.

The gel composition can applied from a single dose product or by use ofa multiple use dispenser which governs the amount of material appliedonto a unit area. In this regard, the dispenser described in U.S. Pat.No. 5,558,560 (Benedict), is one example of a dispenser suitable fordispensing a viscous composition through use of a squeeze-tube andapplicator tip. In presently preferred circumstances, the dispenser issuited for dispensing a gel composition having a viscosity of 200,000 to500,000 cps (particularly 250,000 to 400,000 cps) and a wet coat weightof 50 to 120 mils at a generally uniform thickness. Other methods forthe controlled dispersal of the gel composition include, by way ofexample, a spray applicator, brush, wipe, swab or solid paddleapplicator, applicators for repeated and intermittent use of the gelcomposition and the like. In most applicators (e.g., those featuring adispensing tip and a squeeze-tube), the gel composition can beconveniently stored at ambient conditions and can be provided in sterileform.

One suitable method 10 for applying the gel composition to the wound orother target site (e.g., abrasions, lacerations, scrapes, punctures, andburns) using an applicator is set out in FIG. 1. At the outset at leastthe area around the target site is cleaned and dried (Step 20). Due tothe conformability and breathability of the dried films of the presentdisclosure, drying the wound itself can be optional, depending on theamount of fluid exiting the wound site. In certain embodiments, a driedfilm may retain up to 1 mL of blood or exudate without detaching fromthe body. For moderate to severe bleeding wounds, the site is typicallycleaned and dried prior to application. A first quantity of gelcomposition in an applicator 12 is dispensed at an area proximate thetarget site 11 and a substantially continuous layer 13 of the gelcomposition is created by drawing the applicator across the target site11 while dispensing the composition from the tip 14 (Step 30). Incertain circumstances, it may be desirable to hold the applicator tip 14above the target site without making contact with the tissue. Suchvertical displacement may not be required for minor scrapes or skinlesions. Once the layer 13 reaches an area proximate the target site(e.g., one spaced from the wound) the applicator is manipulated to severthe connection between the layer 13 and the applicator tip. (Step 40).The user may also sever the connection by hand or other tool. In certainimplementations, the layer 13 possesses dimensions sufficient toentirely cover the target site. Multiple layers, however, may be usedfor larger wounds or smaller applicator tips. In one exemplaryimplementation, the continuous layer 13 has a substantially continuousthickness of about 100 mil as applied. Once the desired amount of gel isdispensed, the composition is allowed to dry to a film (typically 2-5minutes).

Another suitable method for applying the gel composition to a targetsite using an applicator is set out in FIG. 2. Like the method 10 ofFIG. 1, the method 100 of FIG. 2 includes the steps of a) cleaning anddry at least the area around the target site (Step 120); dispensing afirst quantity of gel composition at an area proximate the target site110 and creating a substantially continuous layer 113 of the gelcomposition by drawing the applicator across the target site 110 whiledispensing the composition (Step 130) and severing the connectionbetween the layer 113 and the applicator tip 114. (Step 140). After aperiod of time sufficient for the composition to form a film 115 that isdry to the touch (typically 1 to 2 minutes), the user (or treatingprofessional) may tap the film around the periphery of the target toeffect and enhance a seal around the target. (Step 150). In someembodiments, it may be desirable for the person intending to touch thefilm to first dampening his or her finger. Alternatively, the user (ortreating professional) may wet the finger surface with a topicalantiseptic or antibiotic composition for increased protection againstinfection or contamination. In lieu of finger pressure, surfacedepressing tools may be used such as Q-tips, tongue depressors, and foamapplicators.

One such tool is used in the method 200 depicted in FIG. 3. Like themethod 100 of FIG. 2, the method 200 includes the steps of a) cleaningand dry at least the area around the target site (Step 220); dispensinga first quantity of gel composition at an area proximate the target site210 and creating a substantially continuous layer 213 of the gelcomposition by drawing an applicator 212 across the target site 210while dispensing the composition (Step 230) and severing the connectionbetween the layer 213 and the applicator tip 214. (Step 240). Applicatortip 214 includes a convex surface 218 adjacent the dispensing slot.Instead of finger pressure, the user (or treating professional) may tapthe film around the periphery using the convex surface 218 of theapplicator. (Step 250). Using an applicator tip in this fashion may beadvantageous for certain users and wound types, as the perceived (oractual) contamination attendant use of one's finger may be eliminated.

Suitable applicator tips for applying pressure to the gel composition orfilm are depicted in FIGS. 4 and 5. Each applicator tip 214 includes agenerally frustoconical body 215 having a dispensing slot 216 positionedtowards the top (as oriented) of the tip 214. The dispensing slot 216 isdimensioned to dispense a gel composition having a viscosity of 200,000to 400,000 cps and a wet coat weight of 50 to 120 mils at a generallyuniform thickness. The dispensing slot 216 can be disposed at an acuteor obtuse angle relative to the plane defined by the bottom-mostsurfaces of the body 214. In other implementations, the dispensing slotcan be generally parallel to a plane defined by the bottom most surfacesof the body 214. A ridge 217 projects outwardly from the body 215,displacing a surface 218 away from the body 215. The displaced outersurface 218 allows for the applicator tip 214 to be pressed into a gelcomposition or film without contacting the dispensing slot 215. Theouter surface 218 can include a lens-like, convex structure (FIG. 4) ora rail like, planar structure (FIG. 5). One skilled in the art willrecognize that other geometries and configurations are possible forsurface 218, as well as applicator tip body 215. The applicator tip 214may be supplied with or without a cap 219 used to cover the dispensingslot when the applicator is not in use.

Yet another suitable method 300 for applying a gel composition of thepresent disclosure to a target site is disclosed in FIG. 6. While atleast the area surrounding the target is again dried, the substantiallycontinuous layer 313 is not drawn over the target. Instead, in Step 330,a first quantity of gel composition is dispensed at an area proximatethe target site 311 and a substantially continuous layer 313 of the gelcomposition is created by drawing the applicator along the periphery ofthe target site the target site 311 while dispensing the compositionfrom the tip 314. After severing the connection between the layer andthe applicator (Step 340), the resulting layer 313 is drawn across thetarget site and pressed on the opposite side of the target site from theoriginal location of layer 313. (Step 350). The composition can be drawnby hand (as depicted) or by suitable tool.

The gel composition need not be applied in direct contact with theentire target site. In certain implementations, the gel composition maybe applied over an antiseptic or antimicrobial composition, sutures,gauze, other topical compositions, and combinations thereof.

As referenced above, the applied gel compositions of the presentdisclosure can be removed with relatively little force in a singlecontinuous film without substantial desquamation of the underlyingtissue. This desirable property can be enhanced by rolling the edges ofthe applied film toward the center of the target (or film itself) priorto removal. Rolling can, in certain circumstances, provide a graspableedge for a user or treating professional to engage and remove the filmfrom the skin. For thinner films (e.g., less than 4 mils), it may besufficient for the film to be removed in multiple pieces.

Objects and advantages of this disclosure are further illustrated by thefollowing examples, but the particular materials and amounts thereofrecited in these examples, as well as other conditions and details,should not be construed to unduly limit this disclosure.

EXAMPLES

Test Methods

Viscosity Test Methods

The viscosities of exemplary formulations were measured using aBrookfield viscometer, model LVT with Brookfield LV spindles (#4). AllExamples were allowed to equilibrate at approximately 22° C. for 24hours prior to measurement. Preferably the smallest spindle and thelowest speed were chosen such that the viscosity was taken at the lowestspeed possible while staying within 10-90% and preferably 20-80% of theviscometer range. In all cases the sample size and container geometrywere chosen to ensure that there were no wall effects. By “wall effects”it is meant the viscosity value was not affected by the container andwas essentially equivalent to the viscosity taken in an infinitely largecontainer. For this reason, lower viscosity samples required a largersample size to accommodate the larger spindles. The viscosity of eachsample was taken as the highest relatively stable reading that wasachieved.

The viscosities of the aminosilicone adhesion promoters were taken fromthe manufacturer's data sheets. These values were measured according tothe procedures outlined in Japanese Industrial Standard JIS Z 8803,“Methods for viscosity measurement of liquid” using a Cannon-Fenskeviscometer (available from Cannon Instrument Company, State College,Pa., US, at 25° C.

Polycarbonate Peel Adhesion Test Method

The gel compositions were applied at a 50 mil wet coat weight to apolycarbonate coupon (LEXAN Clear Polycarbonate available from SabicAmericas, Houston, Tex., US). The gel composition samples were appliedto a width of 2.54 cm (1.0 in.), a length of 7.62 cm (3 in.), andallowed to dry overnight (about 24 hrs.) at ambient temperature andpressure. Sample materials were laminated to polyester tape (3M 8043,available from 3M Company, St. Paul, Minn., US) using a 4 pound roller,and a lead edge of the film tape laminate was then peeled from the LEXANcoupon. The samples were removed at 180 degrees at a rate of 30.5cm/minute (12 inches per minute). The peel force was then measured witha load cell in units of grams force.

Skin Adhesion Test Method

The gel compositions to be tested for skin adhesion were applied to theskin of one or more human subjects. The backs of one or more subjectswere washed using soap (in particular, IVORY SOAP) prior to sampleapplication. The gel composition samples were applied to a width of 2.54cm (1.0 in.), a length of 7.62 cm (3 in.), and allowed to dry to a filmthickness of at least 5 mils. Samples were placed on the subject's backpositioned so that the long axis of each sample was orientedperpendicular to the volunteer's spine. The order of application ofsample materials was randomized (i.e., rotational placement) on eachsubject. Sample materials were secured using a 2 kg. (4.5-pound) roller.The samples were removed at 180 degrees at a rate of 30.5 cm/minute (12inches per minute). The peel force was then measured with a load cell inunits of grams force. An initial set of gel compositions were appliedand immediately removed (“T-0”). Another set of samples were applied andallowed to dwell for 24 hours before removal (“T-24”), and another setof samples were applied and allowed to dwell for 48 hours before removal(“T-48”).

Skin Stripping Test Method

The gel compositions to be tested were applied to the skin of one ormore human subjects. The adhesive samples had a width of 2.54 cm (1.0in.) and length of 7.62 cm (3 in.) and a film thickness of at least 5mils. Samples were placed on the subject's back positioned so that thelong axis of each sample was oriented perpendicular to the volunteer'sspine. 4 hours later, the testing sample was removed at 180 degrees at arate of 30.5 cm/minute (12 inches per minute) and immediately coveredwith a fresh liner to prevent the skin facing surface of the film fromcontamination by hand touch or dirt/dust from environment. A randompoint on the surface where the sample that was then peeled off after 4hours (T4), and was analyzed using an infrared transmissivity analyzer(ATR method). The light absorption was measured at a frequency in whichkeratin (protein) is known to absorb (1539 cm⁻¹, 1630 cm⁻¹). Theabsorbance of actual skin was considered 100% and the absorbance of thefilm alone when not applied to the skin was considered 0%. Theabsorbance of keratin that adhered to the surface of the adhesive wasrecorded as a percentage, then an average value was calculated. Thesamples were then tested again after a 24 hour dwell.

Moisture Vapor Transmission Rate—Upright (Dry) MVTR Method

The upright MVTR was measured according to ASTM E-96-80. A 3.8 cmdiameter sample was placed between adhesive-containing surfaces of twofoil adhesive rings, each having a 5.1 cm² elliptical opening. The holesof each ring were carefully aligned. Finger pressure was used to form afoil/sample/foil assembly that was flat, wrinkle free, and had no voidareas in the exposed sample. A 120-ml glass jar was filled withapproximately 50 mL of tap water that contained a couple drops of 0.02%(w/w) aqueous Methylene Blue USP (Basic Blue 9, C.I.52015) solution,unless specifically stated in an example. The jar was fitted with ascrew-on cap having a 3.8 inch diameter hole in the center thereof andwith a 4.45 cm diameter rubber washer having an approximately 3.6 cmhole in its center The rubber washer was placed on the lip of the jarand foil/sample/foil assembly was placed backing side down on the rubberwasher. The lid was then screwed loosely on the jar.

The assembly was placed in a chamber at 40° C. and 20% relative humidityfor four hours. At the end of four hours, the cap was tightened insidethe chamber so that the sample was level with the cap (no bulging) andthe rubber washer was in proper seating position.

The foil sample assembly was removed from the chamber and weighedimmediately to the nearest 0.01 gram for an initial dry weight, W1. Theassembly was then returned to the chamber for at least 18 hours, theexposure time T1 in hours, after which it was removed and weighedimmediately to the nearest 0.01 g for a final dry weight, W2. The MVTRin grams of water vapor transmitted per square meter of sample area per24 hours can then be calculated using the following formula.Upright (Dry) MVTR=(W1−W2)×(4.74×10⁴)/T1Moisture Vapor Transmission Rate—Inverted (Wet) MVTR Method

The inverted MVTR was measured using the following test procedure. Afterobtaining the final “dry” weight, W2, as described for the upright MVTRprocedures, the assembly was returned to the chamber for a least 18additional hours of exposure time, T2, with the jars inverted so thatthe tap water was in direct contact with the test sample. The sample wasthen removed from the chamber and weighed to the nearest 0.01 gram for afinal wet weight, W3. The inverted wet MVTR in grams of water vaportransmitted per square meter of sample area per 24 hours can then becalculated using the following formula.Inverted (Wet) MVTR=(W2−W3)×(4.74×10⁴)/T2Antimicrobial Efficacy Test Method

The procedures summarized below as 1) Bactericidal Assay and 2)Bacteriostatic Assay were used for the microbiological assessment ofsubsequent examples of antiseptic gel compositions. The AntimicrobialEfficacy Test includes either the Bactericidal Assay, the BacteriostaticAssay, or both.

The following materials were used in the microbiological test procedure:Tryptic Soy Broth (TSB), available from Becton, Dickinson and Company(BD) of Franklin Lakes, N.J. (USA), under the tradename BACTO; D/ENeutralizing Broth, available from BD under the tradename DIFCO; FBS(Fetal Bovine Serum), Certified, available from Gibco by LiveTechnologies; Phosphate Buffer Saline (PBS) solution; BD Falcon 50 mLPolypropylene Conical Test Tubes, available from BD; Mini Flip-Top Vialwith Butterfields Buffer, available from 3M Company of St. Paul, Minn.(USA); and PETRIFILM Aerobic Count Plate (AC) 6400/6406/6442, availablefrom 3M Company of St. Paul, Minn. (USA).

Cultures of Staphylococcus aureus (ATCC No. 6538), Escherichia coli(ATCC No. 25922), and Pseudomonas aeruginosa (ATCC No. 9027) in 20 mL ofTSB were obtained fresh, overnight (18-24 hours).

Antimicrobial Efficacy—Bactericidal Assay Procedure:

Antiseptic gel solutions were prepared by diluting the concentrated gel(solids 20%-27%) in 1:1 ratio with the appropriate solvent (isooctane orHMDS) to a final volume of 8 mL. The test solutions were prewarmed to32° C. in a heating plate while being stirred. 1 mL of serum and 1 mL ofappropriate bacterial test culture was pipetted into the 8 mL of testsample. The samples were vortex mixed for 30 seconds, then incubated at32° C. for 10 min. Duplicates of 1 mL sample aliquots were removed andmixed into 9 mL of D/E neutralizing broth in 50 mL conical tubes thatwere previously filled. The samples were vortex mixed for 30 seconds athigh speed, then placed into an ice bath. The neutralized samples werediluted with a 1:10 serial dilution using the 9 mL Butterfields Buffertest tubes. The dilutions were completed by adding 1 mL of the samplefluid into 9 mL of Butterfields Buffer for the 1:10 dilution. Next, 1 mLfrom the 1:10 dilution tube was pipetted into 9 mL of ButterfieldsBuffer to make the 1:100 dilution. Then, pipetted 1 mL from the 1:100dilution tube into 9 mL of Butterfields Buffer for a 1:1000 dilution.Finally, pipetted 1 mL from the 1:1000 dilution tube into 9 mL ofButterfields Buffer for a 1:10000 dilution. The samples were plated byvortexing the diluted samples and pipetting 1 mL aliquots from thesetubes onto the PETRIFILM Aerobic Count Plates. The plating process wascompleted to negative five (−5) dilutions, which are also notated as1:1, 1:10, 1:100, 1:1000, 1:10000. The samples were placed in a 37°incubator for 24 hours, then, read with a PETRIFILM PLATE READER(available from 3M Company of St. Paul, Minn.) and the number ofcolonies recorded and reported as Log(10) Recovery. Log(10) Reductionwas also calculated and reported. Log Reduction is calculated bysubtracting the log recovered from the control, which in this case is an8 mL PBS solution inoculated with 1 mL of the same bacterial suspensionand 1 mL of FBS.

2. Antimicrobial Efficacy—Bacteriostatic Assay Procedure:

Antiseptic gel solutions were prepared by diluting the concentrated gel(solids 20%-27%) in 1:1 ratio with the appropriate solvent (isooctane orHMDS) to a final volume of 8 mL. The test solutions were prewarmed to32° C. in a heating plate while being stirred. 1 mL of serum and 1 mL ofappropriate bacterial test culture was pipetted into the 8 mL of testsample. 1 mL aliquots were pipetted from this test mixture and placedinto duplicate flasks containing 100 mL of TSB without neutralizers andmixed well. These samples were incubated at 37° C. for 48 hours. Thesamples were then diluted with a 1:10 serial dilution using theButterfields Buffer test tubes. The dilutions were completed by adding 1mL of the sample fluid into 9 mL of Butterfields Buffer for the 1:10dilution. Next, 1 mL from the 1:10 dilution tube was pipetted into 9 mLof Butterfields Buffer to make the 1:100 dilution. Then, pipetted 1 mLfrom the 1:100 dilution tube into 9 mL of Butterfields Buffer for a1:1000 dilution. Finally, pipetted 1 mL from the 1:1000 dilution tubeinto 9 mL of Butterfields Buffer for a 1:10000 dilution. The sampleswere plated by vortexing the diluted samples and pipetting 1 mL aliquotsfrom these tubes onto the PETRIFILM Aerobic Count Plates. The platingprocess was completed to negative five (−5) dilutions, which are alsonotated as 1:1, 1:10, 1:100, 1:1000, 1:10000. The samples were placed ina 37° incubator for 24 hours, then, read with a PETRIFILM PLATE READER(available from 3M Company of St. Paul, Minn.) and the number ofcolonies recorded and reported as Log(10) Reduction. Log Reduction iscalculated by subtracting the log recovered from the input control,which is an 8 mL PBS solution inoculated with 1 mL of the same bacterialsuspension and 1 mL of FBS.

Preparation of Exemplary Compositions

The materials used in the following examples are summarized in Table 1.

TABLE 1 Summary of materials. Material Description Source SiliconePoly(diorganosiloxane)-polyoxamide copolymer — Polyoxamide made from adiamine of 25,000 molecular weight as (SPOx) per “Preparatory Example 1”of U.S. Pat. No. 7,947,376. HMDS Hexamethyldisiloxane Wacker Chemical,Chicago, IL, US ISO Isooctane Ineos Group AG, Rolle, Switzerland MQSilicate tackifying resin Wacker Chemical, Chicago, IL g-PEICrosslinked, Guanidinylated polyethylenimine Preparatory Example 1 BelowBZT Benzylthonium Chloride, 97% Alfa Aesar, Ward Hill, MA, US PDMSMonocarboxydecyl terminated Gelest, Inc., Morrisville,polydimethylsiloxane fluid, silicone surfactant PA, US R 8200 HMDStreated fumed silica Evonik Corp., Piscataway, NJ, US Kaolin KA105,china clay powder Spectrum Chemical MFG. Corp., New Brunswick, NJ, USSensiva SC10 1,2-octanediol, 3-[(2-ethylhexyl)oxy]-1,2- Schülke & MayrGmbH, propanediol Germany NSNF Non-silicone non-fluorinated release filmDescribed in US2009/0000727 KF-393 Diamino-modified silicone fluid,amine # >280 Shin-Etsu Silicones, Akron, OH, US KF-880 Diamino-modifiedsilicone fluid, amine #56 Shin-Etsu Silicones, Akron, OH, US KF-865 Monoamino-modified silicone fluid, amine # 20 Shin-Etsu Silicones, Akron,OH, US KF-864 Mono amino-modified silicone fluid, amine # 29 Shin-EtsuSilicones, Akron, OH, US KF-859 Mono amino-modified silicone fluid,amine #17 Shin-Etsu Silicones, Akron, OH, US CA-1240 Siliconequatemium-12 Phoenix Chemical, Somerville, NJ AD-3640 Siliconequatemium-8 Phoenix Chemical, Somerville, NJ, US PHMB COSMOCIL CQpolyaminopropyl biguanide Lonza, Overland Park, KS, US

All formulation components are reported in percent weight/weight (%wt/wt) unless otherwise noted.

Preparatory Example 1

Synthesis Steps for Making Cross-Linked Guanylated Polyethylenimine(2-PEI)

A 12 L 3 neck split top resin flask was charged with 1250 g of aqueouspolyethylenimine solution (mw 75,000, 32.6% solids, BASF Lupasol PS)followed by 1279 g of DI water. The flask was equipped with an overheadstirrer and 291.6 g O-methyl isourea hemisulfate was added and themixture was stirred overnight. An aliquot was taken from the viscoussolution and checked by 1H NMR (CD3OD—deuterated methanol) to monitorthe disappearance of the O-methyl isourea hemisulfate. The solution wastransferred to a polypropylene bottle rinsing with a little waterfollowed by measuring percent solids (21.1% by Ohaus).

The solution was then treated with 3401 g of heptanes and stirred for 5minutes. 1,4-Butanediol diglycidyl ether (BUDGE, 91.5 g) was and thesolution was stirred over night (16 hours). Stirring ceased and theheptane and DI water was removed from solution with a vacuum filterstick (coarse porosity). The resulting gel was washed with IPA to drawoff remaining heptane. 2176 g of isopropyl alcohol was added to theflask. The composition was stirred vigorously for 10 minutes and thenfiltered using the filter stick. This procedure was repeated three moretimes. The resulting white solid was then filtered using a nutschefilter and dried in a vacuum oven at 100° C.

The dried beads are then jet milled using a 3000 rpm Model 100/20 jetmiller. The dried beads are placed in a hopper then feed into an airstream tube. The air stream carries the beads to a splitter where thebeads are pushed through two smaller tubes and eventually forced througha cone shaped nozzles (jets). The jets are positioned so the beadscolloid into each other, the impact reduces the particle size. After thecollision the air stream carries the bead particles to a classifier. Theclassifier, depending on its rotational speed will allow small particlesto be collected while larger particles are returned to the air stream tobe jet milled again. Generally the higher classifier speed results infiner particle size.

Gel Composition Sample Preparation

The following steps were used in creating all gel compositions in theExamples below. PDMS was pipetted using a 2 mL pipette into a 125 mLclear glass jar. HMDS was added to the solution jar which was thencapped to prevent evaporation. MQ, g-PEI, Sensiva SC10, and BZT weresubsequently added in that order to the reaction jar. During addition ofthe g-PEI, the material was crushed in a weighing dish with a spatula toremove clumps. The mixture solution was placed in an ice bath (4° C.),where the solution was dispersed using a Polytron PT 2500E (availablefrom Kinematica, Inc., Bohemia N.Y.) for 20 minutes at 18.5×1000 RMP.After dispersion, a stir bar was added to the solution jar which wasthen placed in a hot water bath (66° C.) on a heating and stirringmantle. SPOx was then added immediately and the jar capped. The solutionwas mixed for 2 hours. After two hours, the jar was sealed with SCOTCHThread Sealant Tape (available from 3M Company, St. Paul, Minn.) andplaced on a roller.

Comparative Examples CE1-CE3

Comparative Examples CE1-CE3 were formulated to examine both the Uprightand Inverted MVTR of a dried film. The weight percent of components usedin the formulations for the gel compositions of CE1-CE3 are shown inTable 2A below. To prepare film samples, the gel composition wasapplied, using a syringe, to a polyethylene film clamped down to a flatglass panel. A Gardco Microm II adjustable micrometer film applicator,set to a specific (e.g., 50 mil) thickness, was pulled across the gel toform a thin layer. The films were dried in a hood for 20 minutes andthen die cut to produce circular, 3.8 cm diameter samples. ComparativeExample CE4 is a NEXCARE TEGADERM Waterproof Transparent Dressing,available from 3M Company, St. Paul, Minn.

All MVTR data shown use this test condition and reported with the unitof g/m²/24 hours. The coating thickness for each of the samples was 50mils. The samples were tested and the results are shown in Table 2B.

TABLE 2A Composition of Comparative Examples CE1-CE3. CE1 CE2 CE3 WetDry Wet Dry Wet Dry Components (Gel) (Film) (Gel) (Film) (Gel) (Film)SPOx 17.61 70.45 15.00 60.01 12.39 49.58 g-PEI 0.75 2.99 2.99 11.95 5.2320.90 PDMS 0.37 1.49 1.49 5.97 2.61 10.45 BZT 0.20 0.80 0.20 0.80 0.200.80 Sensiva SC10 1.00 4.00 1.00 4.00 1.00 4.00 MQ 5.07 20.27 4.32 17.273.57 14.27 HMDS 75.00 0.0 75 0.0 75 0.0 Total Wt. % 100.0 100.0 100.0100.0 100.0 100.0 % Solids 25 100 25 100 25 100Multiple samples of the Examples below were measured for Upright (Dry)and Inverted (Wet) MVTR according to the test methods described above.The average results are reported below, followed by the standarddeviation (+/−) of the multiple samples.

TABLE 2B MVTR of Comparative Examples CE1-CE3 Comparative Example CE1CE2 CE3 Upright MVTR (±95% 627 (±54)  728 (±72)  783 (±57) confidence)Inverted MVTR ((±95% 648 (±115) 956 (±124) 1020 (±163) confidence)

Comparative Examples CE4-CE7

A variety of different coating weights of the formulation of ComparativeExample CE2 were tested to examine the impact of coating weight and filmthickness on moisture transmission. The coating weight for each of thesample, as well as the resulting film thickness is Comparative ExamplesCE4-CE7 are shown in Table 3 below. Multiple samples of the Examplesbelow were measured for Upright (Dry) and Inverted (Wet) MVTR accordingto the test methods described above. The average results are reportedbelow, followed by the standard deviation (+/−) of the multiple samples.

TABLE 3 MVTR of Comparative Examples CE4-CE7 Example CE4 CE5 CE6 CE7Coating thickness (mil) 25 50 100 200 Film Thickness (mil)  3  6  13  26Upright MVTR (±95% 1229 (±132) 728 (±72)  353 (±56)  220 (±45)confidence) Inverted MVTR (±95% 1446 (±123) 956 (±124) 569 (±196) 231(±69) confidence)

Comparative Examples CE8-CE13

Comparative Examples CE8-CE13 was conducted to evaluate theantimicrobial efficacy of various gel formulations with BZT. The weightpercent of components used in the formulations for the gel compositionsamples of Comparative Examples CE8-CE13 are shown in Table 4 below.Example 13 is the control Phosphate Buffer Saline (PBS) solution.

TABLE 4 Antimicrobial efficacy of Comparative Examples CE8-CE13Components CE8 CE9 CE10 CE11 CE12 CE13 SPOx 15.35 15.35 15.29 15.2916.07 0.0 g-PEI 4.42 4.42 4.41 4.41 2.43 0.0 PDMS 2.21 2.21 2.20 2.201.22 0.0 BZT 0.10 0.10 0.20 0.20 0.2 0.0 Sensiva SC10 1.0 1.0 1.0 1.0 10.0 MQ 4.42 4.42 4.40 4.40 4.4 0.0 Kaolin 0.0 0.0 0.0 0.0 0.54 0.0 R82000.0 0.0 0.0 0.0 1.65 0.0 ISO 0.0 0.0 0.0 0.0 72.5 0.0 HMDS 75.50 75.575.5 75.5 0.0 0.0 PBS 0 0 0 0 0 100.0 Total Wt. % 100.0 100.0 100.0100.0 100.0 100.0 Dilution 1:1 1:3 1:1 1:3 1:1 Ave. Log Recovery at 10<1 <1 <1 <1 <1 6.36 minutes (E. Coli) Std Dev (at 10 min) 0 0 0 0 0 0.15(E. Coli) Ave. Log Recovery at 10 1.57 1.78 <1 <1 1.15 6.57 minutes (S.aureus) Std Dev (at 10 min) 0.57 0.3 0 0 0.15 0.04 (S. aureus) Ave. LogRecovery at 10 1.57 3.62 <1 3.31 <1 6.73 minutes (P. aeurginosa) Std Dev(at 0 min) 0.27 0.13 0 0.8 0 0.01 (P. aeruginosa)

Comparative Examples CE14-CE18

Comparative Examples CE14-CE18 were formulated to examine both thetensile and elongation of dried film generally in accord with ASTMD882-12. The weight percent of components present in the dried films ofComparative Examples CE14-CE18 are shown in Table 5 below. Gelcompositions of the samples were coated on a 1 mil thick NSNF at 50 milswet (the Gardco Microm II applicator set at 51 mils) and allowed to dryovernight at room temperature and pressure. The dried films were razorcut into 1×2 inches strips and tabs on the strips ends were made usingmasking tape. For each sample, the tabs were secured in the grips of aconstant rate tensile tester (Zwick/Roell Z005). Gauge length was set at1″ and cross-head speed was set at 10″/min. The grips were drawn apartuntil the sample ruptured or broke. Each sample was run in triplicate.

TABLE 5 Mechanical Properties of Comparative Examples CE14-CE18Components CE14 CE15 CE16 CE17 CE18 SPOx 67.0 65.5 59.1 59.1 59.1 g-PEI8.3 17.0 8 8 8 BZT 0.0 0.0 0.70 0.70 0.70 PDMS 0.0 0.0 4.0 4.0 4.0 MQ13.0 12.5 0.0 5.5 16.5 Kaolin 0.0 0.0 2.5 2.5 2.5 R8200 12.3 5.0 22.016.5 5.5 Sensiva SC-10 0.0 0.0 3.6 3.6 3.6 Total Wt. % 100.0 100.0 100.0100.0 100.0 Elongation at break (%) 836 631 87 329 979 Ultimate TensileStrength 0.52 0.68 0.71 0.65 0.68 (MPa) Brookfield Viscosity 294,700180,100 113,800 92,800 71,200 (cps)

Examples 1-4 and Comparative Examples CE19-CE23

These Illustrative and Comparative Examples were formulated to examinecertain adhesive properties of dried films featuring potential adhesionpromoters according to the Polycarbonate Peel Adhesion Test Method. Theweight percent of components present in the gel compositions of Example19-26 are shown in Table 6 below. Gel compositions of the samples werecoated on polycarbonate using a Gardco Microm II applicator set at 51mils, and allowed to dry overnight at ambient temperature and pressure.The sample was peeled from the LEXAN coupon at a platen speed of 305millimeters/minute (12 inches/minute) over a length of 2.54 centimeters(1 inch) using an IMASS Slip/Peel Tester (Model SP-2000, available fromIMASS Incorporated, Accord, Mass., US). Each sample was run induplicate, with the average reported in Table 6 below. The amine number,viscosity, and ratio of amine number to viscosity for the aminosiliconeadhesion promoters used in Examples 1, 2, 5 and Comparative ExamplesCE21-CE22 are also provided in Table 6.

TABLE 6 Composition and Peel Adhesion of Examples 1-5 and ComparativeExamples CE19-CE CE19 CE20 Ex. 1 CE21 CE22 Ex. 2 CE23 Ex. 3 Ex. 4 Ex. 5Wet Wet Wet Wet Wet Wet Wet Wet Wet Wet Components (Gel) (gel) (Gel)(Gel) (Gel) (Gel) (Gel) (Gel) (Gel) (Gel) SPOx 16.5 16.5 16.5 16.5 16.516.5 16.4 16.5 16.5 17.0 g-PEI 2.6 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0KF-393 0.0 2.5 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 KF-864 0.0 0.0 2.5 0.00.0 0.0 0.0 0.0 0.0 2.7 KF-859 0.0 0.0 0.0 2.5 0.0 0.0 0.0 0.0 0.0 0.0KF-865 0.0 0.0 0.0 0.0 2.5 0.0 0.0 0.0 0.0 0.0 KF-880 0.0 0.0 0.0 0.00.0 2.5 0.0 0.0 0.0 0.0 PHMB 0.0 0.0 0.0 0.0 0.0 0.0 2.6 0.0 0.0 0.0CA-1240 0.0 0.0 .0 0.0 0.0 0.0 0.0 2.6 0.0 0.0 AD-3640 0.0 0.0 0.0 0.00.0 0.0 0.0 0.0 2.5 0.0 MQ 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 0.0 HMDS77.50 77.5 77.5 77.5 77.5 77.5 77.5 77.5 77.5 80.3 Total Wt. % 100.0100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 Amine No.n/a^(§) >280 29 17 20 56 n/a^(§) n/a^(§) n/a^(§) 29 Viscosity at n/a^(§)70 1700 60 110 650 n/a^(§) n/a^(§) n/a^(§) 1700 25° C. (mm²/sec) AmineNo. to n/a^(§) >4 0.017 0.28 0.18 0.086 n/a^(§) n/a^(§) n/a^(§) 0.017Viscosity Ratio (sec/mm²) Peel 46.4 14.3 136.2* 0.34 2.2 ** 12.3 93.1788.9 ** Adhesion (oz.) ^(§)Not available or not applicable. *One samplegenerated peel values too high to measure ** Both samples generated peelvalues too high to measure

Examples 1, 2, and 5 (all of which included an aminosilicone adhesionpromoter with an amine number greater than 25 and a relatively low aminenumber to viscosity ratio) demonstrated improved peel adhesion ascompared to Comparative Examples CE19 and CE23 (neither of whichincluded an aminosilicone). Comparative Example CE20, which contained anaminosilicone with a high amine number and an amine number to viscosityratio of greater than 4, did not demonstrate sufficient adhesion.Comparative Examples CE21 and CE22, which had an aminosilicone with alow amine number and a relatively low amine number to viscosity ratio,also did not demonstrate sufficient adhesion. A comparison of Examples1, 2, and 5 to Comparative Examples CE19-CE23 demonstrate that gelcompositions that contain aminosilicones having an amine number greaterthan 25 and an amine number to viscosity ratio of less than 1 show animprovement in peel adhesion. Examples 3 and 4, which contained siliconequaternium-12 and silicone quaternium-8, respectively, also demonstratedrelatively high peel adhesion.

The complete disclosures of the patents, patent documents, andpublications cited herein are incorporated by reference in theirentirety as if each were individually incorporated. Variousmodifications and alterations to this invention will become apparent tothose skilled in the art without departing from the scope and spirit ofthis invention. It should be understood that this invention is notintended to be unduly limited by the illustrative embodiments andexamples set forth herein and that such examples and embodiments arepresented by way of example only with the scope of the inventionintended to be limited only by the claims set forth herein as follows.

What is claimed is:
 1. A gel composition for use as a conformable filmbandage, the gel composition comprising: a polydiorganosiloxanepolyamide; an aminosilicone; and a volatile solvent; wherein theaminosilicone is an amine functionalized silicone that contains pendantgroups comprising at least one of a primary amine, a secondary amine, atertiary amine, or a quaternary ammonium group, and wherein a film castfrom the gel composition is self-supporting on a biological substrateand can be peeled off the substrate without substantially compromisingthe integrity of the film such that at least a portion of the film isremovable in a single continuous layer.
 2. The gel composition of claim1, comprising about 5 to about 30 wt. % polydiorganosiloxane polyamide;about 1 to about 35 wt. % aminosilicone; and about 50 to about 80 wt. %volatile solvent, each based on the total weight of the gel composition.3. The gel composition of claim 1, wherein the polydiorganosiloxanepolyamide is a polydiorganosiloxane polyoxamide.
 4. The gel compositionof claim 1, wherein the aminosilicone has an amine number greater than25.
 5. The gel composition of claim 4, wherein the aminosilicone has aratio of amine number to viscosity less than 1.0.
 6. The gel compositionof claim 1, wherein the aminosilicone is selected from the groupconsisting of: aminodimethicones, trimethylsilylamodimethicones,aminoethylaminopropylsiloxane-dimethylsiloxane copolymers, and mixturesthereof.
 7. The gel composition of claim 1, wherein the aminosiliconehas the structure

wherein R is an alkyl containing between 1 and 12 carbons, the blocksbearing the subscripts x and y may be randomly mixed, the total value ofx is from 10 to 5,000, and the total value of y is from 2 to
 20. 8. Thegel composition of claim 1, wherein the aminosilicone has the structure

wherein the blocks bearing the subscripts x and y may be randomly mixed,the total value of x is from 5 to 5,000, the total value of y is from 1to 20, R and R′ may be the same or different, and R and R′ are eachsaturated, linear or branched alkyl groups of 1 to 12 carbon atoms. 9.The gel composition of claim 1, wherein the aminosilicone comprises atleast one silicone quaternary compound selected from the groupconsisting of: silicone quaternium-12, silicone quaternium-8, siliconequaternium-19, silicone quaternium-22, and mixtures thereof.
 10. The gelcomposition of claim 1, further comprising an MQ silicate tackifyingresin.
 11. The gel composition of claim 1, further comprising: anantiseptic agent, wherein the antiseptic comprises at least one ofoctenidine, chlorhexidine salt, alexidine salt, polyhexamethylenebiguanide salt, benzalkonium salt, cetyl pyridinium salt, cetrimoniumsalt, or benzethonium salt, and combinations thereof.
 12. The gelcomposition of claim 1, wherein the volatile solvent is selected fromthe group consisting of volatile linear and cyclic siloxanes, volatilepolydimethylsiloxanes, isooctane, octane, and combinations thereof. 13.The gel composition of claim 1, further comprising a filler, wherein thefiller is at least one of kaolin and fumed silica.
 14. The gelcomposition of claim 1, substantially free of one or both of a tackifierand a coagulant.
 15. A self-supporting film cast from the composition ofclaim 1, wherein the self-supporting film exhibits an elongation of atleast 100% and an ultimate tensile strength of at least 0.3 MPa afterdrying on a biological substrate.
 16. The self-supporting film of claim15, wherein the film exhibits an upright MVTR of at least 300 g/m²/24hours and a Skin Adhesion of at least 50 g/inch and no greater than 900g/inch.
 17. The self-supporting film of claim 15, wherein at least aportion of the self-supporting film has a thickness of at least 2 milsand no greater than 20 mils.
 18. The self-supporting film of claim 17,wherein the self-supporting film comprises: (a) 50-75 wt. %polydiorganosiloxane polyamide; (b) 0.1-30 wt. % filler; and (c) 10-60wt. % aminosilicone, based on the weight of the film.
 19. Theself-supporting film of claim 18, further comprising: about 15 to about35 wt. % tackifier, based on the weight of the self-supporting film.